JP4623283B2 - Silicon composite particles, production method thereof, and negative electrode material for non-aqueous electrolyte secondary battery - Google Patents

Silicon composite particles, production method thereof, and negative electrode material for non-aqueous electrolyte secondary battery Download PDF

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JP4623283B2
JP4623283B2 JP2005076430A JP2005076430A JP4623283B2 JP 4623283 B2 JP4623283 B2 JP 4623283B2 JP 2005076430 A JP2005076430 A JP 2005076430A JP 2005076430 A JP2005076430 A JP 2005076430A JP 4623283 B2 JP4623283 B2 JP 4623283B2
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幹夫 荒又
悟 宮脇
宏文 福岡
一磨 籾井
興一 浦野
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Shin Etsu Chemical Co Ltd
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Description

本発明は、リチウムイオン二次電池用高容量負極活物質として有用とされる珪素複合体粒子、その製造方法、及び非水電解質二次電池用負極材に関する。   The present invention relates to silicon composite particles useful as a high-capacity negative electrode active material for lithium ion secondary batteries, a method for producing the same, and a negative electrode material for nonaqueous electrolyte secondary batteries.

近年、携帯型の電子機器、通信機器等の著しい発展に伴い、経済性と機器の小型化、軽量化の観点から、高エネルギー密度の二次電池が強く要望されている。従来、この種の二次電池の高容量化策として、例えば、負極材料にＶ，Ｓｉ，Ｂ，Ｚｒ，Ｓｎなどの酸化物及びそれらの複合酸化物を用いる方法（特許文献１：特開平５−１７４８１８号公報、特許文献２：特開平６−６０８６７号公報参照）、溶融急冷した金属酸化物を負極材として適用する方法（特許文献３：特開平１０−２９４１１２号公報参照）、負極材料に酸化珪素を用いる方法（特許文献４：特許第２９９７７４１号公報参照）、負極材料にＳｉ2Ｎ2Ｏ及びＧｅ2Ｎ2Ｏを用いる方法（特許文献５：特開平１１−１０２７０５号公報参照）等が知られている。また、負極材に導電性を付与する目的として、ＳｉＯを黒鉛とメカニカルアロイング後、炭化処理する方法（特許文献６：特開２０００−２４３３９６号公報参照）、Ｓｉ粒子表面に化学蒸着法により炭素層を被覆する方法（特許文献７：特開２０００−２１５８８７号公報参照）、酸化珪素粒子表面に化学蒸着法により炭素層を被覆する方法（特許文献８：特開２００２−４２８０６号公報参照）、更には、ポリイミド系バインダーを用いて成膜後焼結する負極の製造方法がある（特許文献９：特開２００４−２２４３３号公報参照）。 In recent years, with the remarkable development of portable electronic devices, communication devices, etc., secondary batteries with high energy density are strongly demanded from the viewpoints of economy and downsizing and weight reduction of devices. Conventionally, as a measure for increasing the capacity of this type of secondary battery, for example, a method of using an oxide such as V, Si, B, Zr, or Sn and a composite oxide thereof as a negative electrode material (Patent Document 1: Japanese Patent Laid-Open No. Hei 5 (1998)). -174818, Patent Document 2: JP-A-6-60867, a method of applying a melted and quenched metal oxide as a negative electrode material (Patent Document 3: JP-A-10-294112), a negative electrode material A method using silicon oxide (see Patent Document 4: Japanese Patent No. 2997774), a method using Si 2 N 2 O and Ge 2 N 2 O as negative electrode materials (Patent Document 5: see Japanese Patent Laid-Open No. 11-102705), etc. It has been known. In addition, for the purpose of imparting conductivity to the negative electrode material, a method in which SiO is mechanically alloyed with graphite and then carbonized (see Patent Document 6: Japanese Patent Laid-Open No. 2000-243396), carbon is deposited on the Si particle surface by chemical vapor deposition. A method of coating a layer (see Patent Document 7: JP 2000-215887 A), a method of coating a carbon layer on the surface of silicon oxide particles by a chemical vapor deposition method (Patent Document 8: refer to JP 2002-42806 A), Furthermore, there is a method for producing a negative electrode that is sintered after film formation using a polyimide binder (see Patent Document 9: Japanese Patent Application Laid-Open No. 2004-22433).

しかしながら、上記従来の方法では、充放電容量が上がり、エネルギー密度が高くなるものの、サイクル性が不十分であったり、充放電に伴う負極膜そのものの容積変化が大きく、また集電体からの剥離などの問題があり、市場の要求特性には未だ不十分であったりし、必ずしも満足でき得るものではなかった。   However, in the above conventional method, although the charge / discharge capacity is increased and the energy density is increased, the cycleability is insufficient, the volume change of the negative electrode film itself due to charge / discharge is large, and peeling from the current collector is performed. However, the required characteristics of the market are still insufficient and cannot always be satisfied.

これを解決する方法として、熱ＣＶＤによる表面炭素コートなどが提案され、効果を挙げている。しかし、現在の正極容量の少なさとのバランスを考慮すると、負極材の充放電容量は現状では実際の市場の要求レベルに対して過大であることから、電池の用途によっては、容量は多少減じたとしても、よりサイクル性の高い材料が求められていた。即ち、珪素ベースのものではあるが、このものよりエネルギー密度を若干抑えても、サイクル性が高い負極活物質が望まれていた。   As a method for solving this problem, surface carbon coating by thermal CVD has been proposed and has been effective. However, considering the balance with the current low capacity of the positive electrode, the charge / discharge capacity of the negative electrode material is currently excessive with respect to the actual demand level of the market. However, a material with higher cycleability has been demanded. In other words, a negative electrode active material having high cycleability is desired, although it is silicon-based but has a slightly lower energy density than this.

特に、特許第２９９７７４１号公報（特許文献４）では、酸化珪素をリチウムイオン二次電池負極材として用い、高容量の電極を得ているが、本発明者らがみる限りにおいては、未だ初回充放電時における不可逆容量が大きかったり、サイクル性が実用レベルに達していなかったりし、改良する余地がある。また、負極材に導電性を付与した技術についても、特開２０００−２４３３９６号公報（特許文献６）では、固体と固体の融着であるため、均一な炭素皮膜が形成されず、導電性が不十分であるといった問題があるし、特開２０００−２１５８８７号公報（特許文献７）の方法においては、均一な炭素皮膜の形成が可能となるものの、Ｓｉを負極材として用いているため、リチウムイオンの吸脱着時の膨張・収縮があまりにも大きすぎて、結果として実用に耐えられず、サイクル性が低下するためにこれを防止するべく充電量の制限を設けなくてはならず、特開２００２−４２８０６号公報（特許文献８）の方法においては、微細な珪素結晶の析出、炭素被覆の構造及び基材との融合が不十分であることより、サイクル性の向上は確認されるも、充放電のサイクル数を重ねると徐々に容量が低下し、一定回数後に急激に低下するという現象があり、二次電池用としてはまだ不十分であるといった問題があった。   In particular, in Japanese Patent No. 2997741 (Patent Document 4), silicon oxide is used as a negative electrode material for a lithium ion secondary battery to obtain a high-capacity electrode. There is room for improvement because the irreversible capacity at the time of discharge is large and the cycle performance has not reached the practical level. In addition, regarding the technique for imparting conductivity to the negative electrode material, in Japanese Patent Application Laid-Open No. 2000-243396 (Patent Document 6), since it is a solid-solid fusion, a uniform carbon film is not formed, and conductivity is improved. There is a problem that it is insufficient, and in the method of Japanese Patent Application Laid-Open No. 2000-215887 (Patent Document 7), although a uniform carbon film can be formed, since Si is used as a negative electrode material, lithium The expansion / contraction at the time of adsorption / desorption of ions is too large, and as a result, it cannot withstand practical use. In the method of 2002-42806 (patent document 8), the precipitation of fine silicon crystals, the structure of the carbon coating, and the fusion with the base material are insufficient, and thus the improvement in cycleability is confirmed. , Gradually decreased capacity Hover the number of cycles of charge and discharge, there is a phenomenon that decreases rapidly after a certain number of times, there is a problem as the secondary battery is still insufficient.

特開平５−１７４８１８号公報JP-A-5-174818 特開平６−６０８６７号公報JP-A-6-60867 特開平１０−２９４１１２号公報JP 10-294112 A 特許第２９９７７４１号公報Japanese Patent No. 2999741 特開平１１−１０２７０５号公報JP-A-11-102705 特開２０００−２４３３９６号公報JP 2000-243396 A 特開２０００−２１５８８７号公報JP 2000-215887 A 特開２００２−４２８０６号公報JP 2002-42806 A 特開２００４−２２４３３号公報Japanese Patent Laid-Open No. 2004-22433

本発明は、上記事情に鑑みなされたもので、よりサイクル性の高いリチウムイオン二次電池の負極の製造を可能とする珪素複合体粒子、その製造方法並びに非水電解質二次電池用負極材を提供することを目的とする。   The present invention has been made in view of the above circumstances, and provides a silicon composite particle capable of producing a negative electrode of a lithium ion secondary battery with higher cycleability, a method for producing the same, and a negative electrode material for a non-aqueous electrolyte secondary battery. The purpose is to provide.

本発明者は、上記目的を達成するため鋭意検討を行った結果、よりサイクル性が高く、かつ珪素系負極活物質での課題であった充放電時の体積変化の低減効果のある非水電解質二次電池負極用の活剤として有効な珪素複合体を見出した。
また、炭素系負極材よりははるかに高いエネルギー密度を有し、珪素そのものの特性である高エネルギー密度という観点では若干低下するものの、従来の珪素系負極材よりサイクル性の高いリチウムイオン二次電池の負極の製造を可能とする珪素−炭素複合体として、サイクル性が高く、かつ充放電時の体積変化の低減効果のある非水電解質二次電池負極用の活剤として有効な珪素−炭素複合体を見出した。 As a result of intensive studies to achieve the above object, the present inventor has a non-aqueous electrolyte that is more cycleable and has an effect of reducing volume change during charge / discharge, which was a problem with a silicon-based negative electrode active material. An effective silicon composite was found as an activator for a secondary battery negative electrode.
In addition, it has a much higher energy density than the carbon-based negative electrode material, and is slightly lower in terms of high energy density, which is a characteristic of silicon itself, but has a higher cycleability than conventional silicon-based negative electrode materials. As a silicon-carbon composite that makes it possible to produce a negative electrode, a silicon-carbon composite that is effective as an activator for a negative electrode of a nonaqueous electrolyte secondary battery that has high cycleability and is effective in reducing volume change during charge and discharge I found my body.

即ち、充放電容量の大きな電極材料の開発は極めて重要であり、各所で研究開発が行われている。このような中で、リチウムイオン二次電池負極活物質として珪素、酸化珪素（ＳｉＯx）、及び珪素系合金はその容量が大きいということで大きな関心を持たれているが、繰り返し充放電をしたときの劣化が大きい、即ちサイクル性に劣ること、また、特に酸化珪素では初期効率が低いことから、ごく一部のものを除き実用化には至っていないのが現状であった。このような観点より、このサイクル性及び初期効率の改善を目標に検討した結果、酸化珪素粉末に熱ＣＶＤにより炭素コートを施すことによって、従来のものと比較して格段にその性能が向上することを見出した（特開２００４−０４７４０４号公報）が、長期安定性、初期効率に更なる改良が求められた。 In other words, the development of electrode materials having a large charge / discharge capacity is extremely important, and research and development are being conducted in various places. Under such circumstances, silicon, silicon oxide (SiO x ), and silicon-based alloys as lithium ion secondary battery negative electrode active materials are of great interest because of their large capacity, but were repeatedly charged and discharged. Since the deterioration at the time is large, that is, the cycle performance is inferior, and the initial efficiency is particularly low in silicon oxide, it has not been put into practical use except for a few. From this point of view, as a result of studying with the goal of improving the cycle performance and initial efficiency, by applying a carbon coat to silicon oxide powder by thermal CVD, its performance is significantly improved compared to the conventional one. (Japanese Patent Laid-Open No. 2004-047404), however, further improvement in long-term stability and initial efficiency has been demanded.

このため、ＣＶＤ法による炭素コート珪素粉及び酸化珪素粉をリチウムイオン二次電池負極の活物質として使用した時に、多回数の充放電後の急激な充放電容量低下の原因について、構造そのものからの検討を行い、解析した結果、リチウムを大量に吸蔵・放出することによって大きな体積変化が起こり、これに伴い粒子の破壊が起こること、更にリチウムの吸蔵によってもともと導電性が小さい珪素及び珪素系合金が体積膨張することによって電極自体の導電率が低下し、更に負極膜の集電体からの剥離などが起こり、結果として集電性の低下によりリチウムイオンの電極内の移動が妨げられ、サイクル性及び効率低下が惹起されることが原因であることがわかった。更に結晶学的に無定形の酸化珪素構造が残った状態では、酸化珪素の酸素がリチウムを酸化リチウムとして捕捉するために初期効率が極めて低くなることが分かった。   For this reason, when carbon-coated silicon powder and silicon oxide powder by CVD are used as the active material of the negative electrode of a lithium ion secondary battery, the cause of the sudden decrease in charge / discharge capacity after many times of charge / discharge is from the structure itself. As a result of investigation and analysis, a large volume change occurs due to insertion and extraction of a large amount of lithium, resulting in the destruction of particles, and furthermore, silicon and silicon-based alloys that originally have low conductivity due to the insertion of lithium. Due to the volume expansion, the conductivity of the electrode itself decreases, and further, the negative electrode film peels off from the current collector, and as a result, the movement of lithium ions in the electrode is hindered due to the decrease in current collection, and the cycle performance and It was found that this was caused by a decrease in efficiency. Furthermore, it was found that in the state where the crystallographically amorphous silicon oxide structure remains, the initial efficiency is extremely low because oxygen of silicon oxide traps lithium as lithium oxide.

そこで、このようなことに基づいて、リチウムの吸蔵・放出に伴う体積変化を緩和して安定な構造について鋭意検討を行った結果、珪素又は珪素合金の微粒子表面を不活性で強固な物質、例えばＳｉ−Ｃ系、Ｓｉ−Ｃ−Ｏ系、Ｓｉ−Ｃ−Ｎ系コンポジットなどで被覆して造粒し、更にこの内部に空隙を有する構造にすることによって、リチウムイオン二次電池負極活物質としての上記問題を解決し、安定して大容量の充放電容量を有し、かつ充放電のサイクル性及び効率を向上させることができることを見出した。従って、珪素及び珪素合金微粒子を高度に架橋できる熱硬化性の有機珪素化合物、例えばハイドロシリレーションによる付加反応性シロキサン組成物、多官能シラン／シロキサン、（ポリ）シラザン、ポリカルボシランなどの中に細かく分散し、熱硬化後、更に不活性雰囲気下で焼結し、無機化後、再粉砕することによってサイクル性などの特性が向上した珪素複合粒子が得られることを見出した。また、この場合、珪素や珪素合金微粒子と有機珪素化合物との密着性を向上させるために、予めその表面にシランカップリング剤などで疎水化処理を施すことも大きな効果があること、更に珪素複合体粒子を得たままの状態では、導電性がないので、導電性の炭素粉との混合で負極活物質として用いられるが、こうして製造される珪素複合体粒子に熱ＣＶＤ処理などにより炭素コートを施すことによって、従来のものと比較して格段にその性能が向上することを見出した。   Therefore, based on the above, as a result of diligent study on the stable structure by reducing the volume change associated with the insertion and extraction of lithium, the surface of the fine particles of silicon or silicon alloy is an inert and strong substance, for example, As a lithium ion secondary battery negative electrode active material, it is granulated by coating with Si-C-based, Si-C-O-based, Si-C-N-based composite, etc. It has been found that the above problems can be solved, the battery can stably have a large charge / discharge capacity, and the cycleability and efficiency of charge / discharge can be improved. Therefore, in thermosetting organosilicon compounds that can highly crosslink silicon and silicon alloy fine particles, such as addition-reactive siloxane compositions by hydrosilylation, polyfunctional silane / siloxane, (poly) silazane, polycarbosilane, etc. It has been found that silicon composite particles having improved cycle characteristics and the like can be obtained by finely dispersing, thermally curing, further sintering in an inert atmosphere, mineralization, and re-grinding. In this case, in order to improve the adhesion between the silicon or silicon alloy fine particles and the organosilicon compound, it is also effective to apply a hydrophobic treatment to the surface with a silane coupling agent in advance. In the state where the body particles are obtained, since there is no conductivity, it is used as a negative electrode active material by mixing with conductive carbon powder. However, the silicon composite particles thus produced are coated with a carbon coat by thermal CVD treatment or the like. It has been found that the performance is remarkably improved as compared with the conventional one.

更に、球状又は鱗片状グラファイト微粒子等の炭素微粒子を核にしてその周囲に珪素又は珪素系合金の微粒子表面を不活性で強固な物質、例えばＳｉ−Ｃ系、Ｓｉ−Ｃ−Ｏ系、Ｓｉ−Ｃ−Ｎ系コンポジットなどで付着して造粒し、更にこの内部に空隙を有する構造にすることによっても、リチウムイオン二次電池負極活物質としての上記問題を解決し、安定して大容量の充放電容量を有し、かつ充放電のサイクル性及び効率を大幅に向上させることができることを見出した。更に珪素−炭素複合体粒子を得たままの状態でも、多少導電性は有することがあるが、こうして製造される珪素−炭素系複合体粒子に熱ＣＶＤ処理などにより更に炭素コートを施すことによって、従来のものと比較して格段にその性能が向上することを見出し、本発明をなすに至った。   Furthermore, carbon fine particles such as spherical or flaky graphite fine particles are used as the core, and the surface of the fine particles of silicon or a silicon-based alloy is inert and strong around them, such as Si—C, Si—C—O, Si— By adhering and granulating with a C—N composite, etc., and further having a void structure inside this, the above problem as the negative electrode active material of the lithium ion secondary battery can be solved, and a stable and large capacity can be obtained. It has been found that it has a charge / discharge capacity and can greatly improve the chargeability / discharge cycleability and efficiency. Furthermore, even if the silicon-carbon composite particles are still obtained, they may have some conductivity, but by further applying a carbon coat to the silicon-carbon composite particles thus produced by thermal CVD treatment, The inventors have found that the performance is remarkably improved as compared with the conventional one, and have made the present invention.

本発明は、珪素、珪素合金又は酸化珪素の微粒子及び炭素微粒子を有機珪素化合物又はその混合物と共に焼結することによって得られる粒子であって、上記有機珪素化合物又はその混合物が焼結されることによって形成される珪素系無機化合物をバインダーとしてこの中に珪素又は珪素合金微粒子及び炭素微粒子が分散されていると共に、該粒子内に空隙が存在する構造を有することを特徴とする、リチウムイオン二次電池用珪素−炭素複合体粒子を提供する。
この場合、珪素、珪素合金又は酸化珪素の一次粒子の大きさが１００ｎｍ〜１０μｍであり、炭素の一次粒子の大きさが１００ｎｍ〜２０μｍであり、珪素系無機化合物がＳｉ−Ｃ−ＯもしくはＳｉ−Ｃ−Ｎ系コンポジット、ＳｉＮx、ＳｉＯy、ＳｉＣz（但し、ｘは０＜ｘ≦４／３、ｙは０＜ｙ≦２、ｚは０＜ｚ≦１の正数である）又はこれらの混合物であることが好ましく、炭素微粒子が球形又は鱗片状の天然又は合成グラファイトであることが好ましい。
 The present invention is a particle obtained by sintering fine particles of silicon, silicon alloy or silicon oxide and carbon fine particles together with an organic silicon compound or a mixture thereof, and the organic silicon compound or a mixture thereof is sintered. A lithium ion secondary battery characterized by having a structure in which silicon or silicon alloy fine particles and carbon fine particles are dispersed in a silicon-based inorganic compound formed as a binder and voids are present in the particles. Silicon-carbon composite particles for use are provided.
In this case, the size of primary particles of silicon, silicon alloy, or silicon oxide is 100 nm to 10 μm, the size of primary particles of carbon is 100 nm to 20 μm, and the silicon-based inorganic compound is Si—C—O or Si—. CN composite, SiN x , SiO y , SiC z (where x is a positive number satisfying 0 <x ≦ 4/3, y is 0 <y ≦ 2, z is 0 <z ≦ 1) or these The carbon fine particles are preferably spherical or scale-like natural or synthetic graphite.

ここで、有機珪素化合物又はその混合物が、架橋基を有する反応性有機珪素化合物又は硬化性ポリシロキサン組成物であることが好ましく、この場合、架橋基を有する反応性有機珪素化合物が、後述する一般式（１）〜（５）で示されるシラン又はシロキサンの１種又は２種以上であるか、平均式ＣhＨiＳｉＯjＮk（ｈ、ｉ、ｊは正数、ｋは０又は正数）で表され、架橋点が珪素原子４個に対して少なくとも１個有し、かつ（ｈ−ｊ）が０より大きなシラン又はシロキサンであること、また、硬化性ポリシロキサン組成物が、付加反応硬化型オルガノポリシロキサン組成物であることが好ましい。
更に、本発明の珪素複合体粒子、珪素−炭素複合体粒子は、粒子内の空隙率が１〜７０体積％であることが好ましく、また表面を炭素でコーティングしてなるものが好ましい。 Here, the organosilicon compound or a mixture thereof is preferably a reactive organosilicon compound having a crosslinking group or a curable polysiloxane composition. In this case, the reactive organosilicon compound having a crosslinking group is generally described later. One or more of silanes or siloxanes represented by formulas (1) to (5), or an average formula C h H i SiO j N k (h, i, j are positive numbers, k is 0 or positive A silane or siloxane having at least one crosslinking point with respect to 4 silicon atoms and (hj) being greater than 0, and a curable polysiloxane composition is added. A reaction curable organopolysiloxane composition is preferred.
Furthermore, the silicon composite particles and silicon-carbon composite particles of the present invention preferably have a porosity in the particles of 1 to 70% by volume, and those obtained by coating the surface with carbon.

本発明は、また、珪素、珪素合金又は酸化珪素の微粒子を有機珪素化合物又はその混合物と共に焼結し、造粒して、上記有機珪素化合物又はその混合物が焼結されることによって形成される珪素系無機化合物をバインダーとしてこの中に珪素又は珪素合金微粒子が分散されていると共に、内部に空隙が存在する構造を有する珪素複合体粒子を得ることを特徴とする珪素複合体粒子の製造方法、及び
珪素、珪素合金又は酸化珪素の微粒子及び炭素微粒子を有機珪素化合物又はその混合物と共に焼結し、造粒して、上記有機珪素化合物又はその混合物が焼結されることによって形成される珪素系無機化合物をバインダーとしてこの中に珪素又は珪素合金微粒子及び炭素微粒子が分散されていると共に、内部に空隙が存在する構造を有する珪素−炭素複合体粒子を得ることを特徴とする珪素−炭素複合体粒子の製造方法を提供する。
この場合、有機珪素化合物又はその混合物が、架橋基を有する反応性有機珪素化合物又は硬化性ポリシロキサン組成物であり、これを珪素又は珪素合金微粒子と混合した後、熱硬化又は触媒反応により硬化させて架橋物とし、更に不活性気流中５００〜１，４００℃の温度範囲で加熱、焼結させて無機化し、これを０．５〜３０μｍに再粉砕することが好ましい。 The present invention also provides silicon formed by sintering fine particles of silicon, a silicon alloy, or silicon oxide together with an organic silicon compound or a mixture thereof, and granulating the organic silicon compound or the mixture thereof. Silicon composite particles having a structure in which silicon or silicon alloy fine particles are dispersed therein and a void is present therein, with a base inorganic compound as a binder, and a method for producing silicon composite particles, Silicon inorganic compound formed by sintering and granulating silicon, silicon alloy or silicon oxide fine particles and carbon fine particles together with an organic silicon compound or a mixture thereof, and sintering the organic silicon compound or the mixture thereof. Silicon-carbon having a structure in which silicon or silicon alloy fine particles and carbon fine particles are dispersed therein and voids exist inside Provided is a method for producing silicon-carbon composite particles characterized by obtaining elementary composite particles.
In this case, the organosilicon compound or a mixture thereof is a reactive organosilicon compound or a curable polysiloxane composition having a crosslinkable group, which is mixed with silicon or silicon alloy fine particles and then cured by thermal curing or catalytic reaction. It is preferable to make it into a crosslinked product, further heat and sinter in an inert air current at a temperature range of 500 to 1,400 ° C. to make it inorganic, and regrind it to 0.5 to 30 μm.

更に、珪素又は珪素合金微粒子の表面を予めシランカップリング剤、その（部分）加水分解縮合物、シリル化剤、シリコーンレジンから選ばれる１種又は２種以上の表面処理剤で処理することが好ましい。また、上記の製造方法によって得られた複合体粒子を有機物ガス及び／又は蒸気を含む雰囲気下、８００〜１，４００℃の温度域で熱処理して、上記複合体粒子の表面をコーティングすることが好ましい。   Furthermore, it is preferable to treat the surface of the silicon or silicon alloy fine particles in advance with one or more surface treatment agents selected from silane coupling agents, (partial) hydrolysis condensates, silylating agents, and silicone resins. . In addition, the composite particles obtained by the above production method may be heat-treated at a temperature range of 800 to 1,400 ° C. in an atmosphere containing an organic gas and / or vapor to coat the surface of the composite particles. preferable.

本発明は、更に上記珪素複合体粒子又は珪素−炭素複合体粒子を用いた非水電解質二次電池用負極材を提供する。
この場合、珪素複合体粒子又は珪素−炭素複合体粒子と導電剤の混合物であって、混合物中の導電剤が１〜６０質量％であり、かつ混合物中の全炭素量が２５〜９０質量％である混合物を用いた非水電解質二次電池用負極材であることが好ましい。 The present invention further provides a negative electrode material for a non-aqueous electrolyte secondary battery using the silicon composite particles or silicon-carbon composite particles.
In this case, it is a mixture of silicon composite particles or silicon-carbon composite particles and a conductive agent, the conductive agent in the mixture is 1 to 60% by mass, and the total carbon content in the mixture is 25 to 90% by mass. It is preferable that it is a negative electrode material for nonaqueous electrolyte secondary batteries using the mixture which is.

本発明の珪素複合体及び珪素−炭素複合体粒子は、非水電解質二次電池用負極材として用いられて、良好なサイクル性を与える。   The silicon composite and silicon-carbon composite particles of the present invention are used as a negative electrode material for a non-aqueous electrolyte secondary battery and give good cycle characteristics.

以下、本発明につき更に詳しく説明する。
本発明は、リチウムイオン二次電池用負極活物質として、充放電容量が現在主流であるグラファイト系のものと比較して、その数倍の容量であることから期待されている反面、繰り返しの充放電による性能低下が大きなネックとなっている珪素系負極材のサイクル性及び効率を改善した珪素複合体粒子を提供するもので、珪素、珪素合金又は酸化珪素の微粒子を有機珪素化合物又はその混合物と焼結することによって得られた（結果として造粒された）、珪素又は珪素合金の微粒子がバインダーとしての珪素系無機化合物に分散し、かつその内部に空隙を有する構造を持つ、好ましくは平均粒径が０．５〜３０μｍの粒子状のものである。図１はこれを示すもので、図１において、１は珪素複合体粒子であり、１１は珪素又は珪素合金、１２は珪素系無機化合物のバインダー、１３が空隙である。また、その粒子表面を好ましくはその少なくとも一部がカーボンと融合した状態でカーボンがコーティング（融着）してなるものである。
また、本発明は、サイクル性及び効率を改善し、更に充放電に伴う大きな体積変化を緩和した珪素−炭素系複合体を提供するもので、珪素、珪素合金又は酸化珪素の微粒子及び炭素微粒子を有機珪素化合物又はその混合物と共に焼結することによって得られた（結果として造粒された）炭素微粒子、好ましくは球状又は鱗片状炭素微粒子を核にして、珪素又は珪素合金の微粒子を、珪素系無機化合物をバインダーとして分散し、かつその内部に空隙を有する構造を有する好ましくは平均粒径が０．５〜３０μｍの粒子状のものである。図２は、これを示すもので、２は珪素−炭素複合体粒子であり、１１，１２，１３は上記の通り、１４は炭素微粒子である。また、その表面の導電性を増すために，熱ＣＶＤによりカーボンコートしてもよい。 Hereinafter, the present invention will be described in more detail.
The present invention is expected as a negative electrode active material for a lithium ion secondary battery because its charge / discharge capacity is several times that of the current mainstream graphite-based material, but it is repeatedly charged. Disclosed is a silicon composite particle having improved cycle performance and efficiency of a silicon-based negative electrode material in which performance deterioration due to discharge is a major bottleneck. Silicon, silicon alloy or silicon oxide fine particles are combined with an organic silicon compound or a mixture thereof. Obtained by sintering (as a result of granulation), silicon or silicon alloy fine particles are dispersed in a silicon-based inorganic compound as a binder and have a structure having voids therein, preferably average particles It is in the form of particles having a diameter of 0.5 to 30 μm. FIG. 1 shows this. In FIG. 1, 1 is a silicon composite particle, 11 is silicon or a silicon alloy, 12 is a binder of a silicon-based inorganic compound, and 13 is a void. The particle surface is preferably coated (fused) with carbon in a state where at least a part of the particle surface is fused with carbon.
In addition, the present invention provides a silicon-carbon composite in which cycleability and efficiency are improved and a large volume change associated with charge / discharge is alleviated. Silicon, silicon alloy or silicon oxide fine particles and carbon fine particles are provided. Carbon fine particles obtained by sintering together with an organosilicon compound or a mixture thereof (as a result of granulation), preferably spherical or scaly carbon fine particles, and silicon or silicon alloy fine particles as silicon-based inorganic It is preferably in the form of particles having a structure in which a compound is dispersed as a binder and voids are contained therein, preferably having an average particle size of 0.5 to 30 μm. FIG. 2 shows this, in which 2 is silicon-carbon composite particles, 11, 12 and 13 are as described above, and 14 is carbon fine particles. Moreover, in order to increase the conductivity of the surface, carbon coating may be performed by thermal CVD.

また、本発明の珪素複合体及び珪素−炭素複合体は、下記性状を有していることが好ましい。
ｉ．銅を対陰極としたＸ線回折（Ｃｕ−Ｋα）において、２θ＝２８．４°付近を中心としたＳｉ（１１１）に帰属される回折ピークが観察され、その回折線の広がりをもとに、シェーラーの式によって求めた結晶の粒子系が、原料によってその大きさは異なるが、２ｎｍ以上、特に５ｎｍ以上である、
ｉｉ．リチウムイオン二次電池負極において、リチウムイオンを吸蔵・放出しうるゼロ価の珪素が、炭化珪素微粉末中遊離珪素を測定する方法であるＩＳＯ ＤＩＳ ９２８６に準じた方法である、水酸化アルカリを作用させる時に水素が生成することによって水素発生量として測定ができ、水素発生量から換算して得られるゼロ価の珪素量が１〜９０質量％、好ましくは２０〜９０質量％であり、
ｉｉｉ．走査電子顕微鏡観察において、粒子内部の観察を行ったときに、空隙が観察される構造である。 Moreover, it is preferable that the silicon composite and silicon-carbon composite of the present invention have the following properties.
i. In X-ray diffraction (Cu-Kα) using copper as the counter-cathode, a diffraction peak attributed to Si (111) centered around 2θ = 28.4 ° is observed, and based on the broadening of the diffraction line The particle system of the crystal obtained by the Scherrer equation is 2 nm or more, particularly 5 nm or more, although the size varies depending on the raw material.
ii. In a lithium ion secondary battery negative electrode, zero-valent silicon capable of occluding and releasing lithium ions is a method according to ISO DIS 9286, which is a method for measuring free silicon in silicon carbide fine powder. When hydrogen is generated, it can be measured as a hydrogen generation amount, and a zero-valent silicon amount obtained by conversion from the hydrogen generation amount is 1 to 90% by mass, preferably 20 to 90% by mass,
iii. In the scanning electron microscope observation, the voids are observed when the inside of the particle is observed.

本発明において、カーボンコーティング（融着）しているとは、層状に整列したカーボン層と、内部の珪素複合体との間に炭素と珪素が共存し、かつ、双方が界面部において融合している状態を示し、透過電子顕微鏡（図３参照）で観察することができる。   In the present invention, carbon coating (fused) means that carbon and silicon coexist between a layered carbon layer and an internal silicon composite, and both fuse at the interface. And can be observed with a transmission electron microscope (see FIG. 3).

ここで、珪素微粒子としては、純度が９５％以上（即ち、９５〜１００％）、特に９９．０％以上（即ち、９９．０〜１００％）のものが好ましい。また、珪素微粒子としては、一般式ＳｉＯx（１≦ｘ＜１．６）で表される酸化珪素粉末を予め５００〜１，２００℃、好ましくは５００〜１，０００℃、より好ましくは５００〜９００℃の温度域で有機物ガス及び／又は蒸気で化学蒸着処理したものを原料として、不活性ガス雰囲気下１，０００〜１，４００℃、好ましくは１，１００〜１，３００℃の温度域で熱処理を施して珪素と二酸化珪素に不均化することによって得られる珪素微粒子を用いることもできる。また、酸化珪素を有機珪素化合物と共に焼結することで、この焼結時に珪素微粒子を不均化、形成してもよい。 Here, the silicon fine particles preferably have a purity of 95% or more (that is, 95 to 100%), particularly 99.0% or more (that is, 99.0 to 100%). As the silicon fine particles, silicon oxide powder represented by the general formula SiO x (1 ≦ x <1.6) is preliminarily 500 to 1,200 ° C., preferably 500 to 1,000 ° C., more preferably 500 to The raw material is a material vapor-deposited with an organic gas and / or vapor in a temperature range of 900 ° C. Under an inert gas atmosphere, 1,000 to 1,400 ° C., preferably 1,100 to 1,300 ° C. Silicon fine particles obtained by heat treatment to disproportionate to silicon and silicon dioxide can also be used. Further, by sintering silicon oxide together with an organic silicon compound, silicon fine particles may be disproportionated and formed during the sintering.

これら珪素、珪素合金、酸化珪素の一次粒子の大きさは、レーザー光回折法による粒度分布測定法で平均粒子径（例えば累積重量が５０％となる粒子径Ｄ50又はメジアン径）が１００ｎｍ〜１０μｍ、より好ましくは１００ｎｍ〜７μｍ、更に好ましくは１〜５μｍで、特に粒子径が均一であることが好ましい。 The primary particles of silicon, silicon alloy, and silicon oxide have an average particle size (for example, a particle size D 50 or a median size with a cumulative weight of 50%) measured by a particle size distribution measurement method using a laser beam diffraction method. More preferably, the particle diameter is 100 nm to 7 μm, more preferably 1 to 5 μm, and the particle diameter is particularly uniform.

一方、珪素−炭素複合体粒子を得る場合に用いる炭素微粒子の一次粒子の大きさは上記と同様の測定法により１００ｎｍ〜２０μｍ、より好ましくは１〜２０μｍ、更に好ましくは３〜１０μｍであり、同様に粒子径が均一であることが好ましい。なお、炭素微粒子は電極膜の成膜性及びリチウムの吸蔵・放出能などの点から球形又は鱗片状の天然又は合成グラファイトが好ましい。   On the other hand, the size of the primary particles of the carbon fine particles used for obtaining the silicon-carbon composite particles is 100 nm to 20 μm, more preferably 1 to 20 μm, still more preferably 3 to 10 μm by the same measurement method as above. The particle diameter is preferably uniform. The carbon fine particles are preferably spherical or scale-like natural or synthetic graphite from the viewpoint of the film formability of the electrode film and the ability to absorb and release lithium.

珪素−炭素複合体粒子を得る際の上記珪素又は珪素合金微粒子と炭素微粒子との割合は、質量比として９０：１０〜２０：８０、特に８０：２０〜４０：６０が好ましい。炭素量が少なすぎると、サイクル性が劣り、多すぎると、単位容積当りの充放電容量（又はエネルギー密度）の低下を招く。なお、酸化珪素微粒子と炭素微粒子との割合は、この酸化珪素微粒子から得られる珪素微粒子と炭素微粒子との割合が上記のようになるように選定される。   The ratio of the silicon or silicon alloy fine particles to the carbon fine particles in obtaining the silicon-carbon composite particles is preferably 90:10 to 20:80, particularly 80:20 to 40:60 as a mass ratio. If the amount of carbon is too small, the cycleability is inferior, and if it is too large, the charge / discharge capacity (or energy density) per unit volume is reduced. The ratio between the silicon oxide fine particles and the carbon fine particles is selected so that the ratio between the silicon fine particles and the carbon fine particles obtained from the silicon oxide fine particles is as described above.

一方、バインダーとしての珪素系無機化合物としては、後述する有機珪素化合物又はその混合物を焼結することによって形成されたＳｉ−Ｃ−Ｏ系コンポジット、Ｓｉ−Ｃ−Ｎ系コンポジット、ＳｉＮx、ＳｉＯy、ＳｉＣz又はこれらの混合物が挙げられる。なお、ｘは０＜ｘ≦４／３、好ましくは０．１≦ｘ≦４／３の正数であり、ｙは０＜ｙ≦２、好ましくは０．１≦ｙ≦２の正数であり、ｚは０＜ｚ≦１、好ましくは０．１≦ｚ≦１の正数である。 On the other hand, as the silicon-based inorganic compound as the binder, a Si—C—O-based composite, a Si—C—N-based composite, SiN x , SiO y formed by sintering an organic silicon compound or a mixture thereof described later. , SiC z or a mixture thereof. Note that x is a positive number 0 <x ≦ 4/3, preferably 0.1 ≦ x ≦ 4/3, and y is a positive number 0 <y ≦ 2, preferably 0.1 ≦ y ≦ 2. And z is a positive number of 0 <z ≦ 1, preferably 0.1 ≦ z ≦ 1.

具体的にＳｉ−Ｃ−Ｏ系コンポジットとしては、珪素、珪素合金、酸化珪素の微粒子を、高度に架橋し得るオルガノポリシロキサン（例えば付加硬化型、縮合硬化型等の硬化性オルガノポリシロキサン組成物等）でコート後、不活性雰囲気下、高温で焼成し、無機化することによって得ることができる。
Ｓｉ−Ｃ−Ｎ系コンポジットとしては、上記のオルガノポリシロキサンに代えて、高度に架橋し得る含窒素オルガノポリシロキサン（例えば付加硬化型、縮合硬化型等のアミノ変性オルガノポリシロキサン組成物）及び／又はオルガノポリシラザンを用いて同様に焼成、無機化することによって得ることができる。
ＳｉＮxとしては、ポリカルボシランをコート後、アンモニア雰囲気下で同様に焼成、無機化することによって得ることができる。
ＳｉＯyとしては、テトラアルコキシシラン等をコートし、硬化させた後、同様に焼成、無機化することによって得ることができる。
ＳｉＣzとしては、テトラアルキルシラン等をコートし、硬化させた後、同様に焼成、無機化することによって得ることができる。
なお、Ｓｉ−Ｃ−Ｏ系コンポジット、Ｓｉ−Ｃ−Ｎ系コンポジットとは、それぞれ珪素、炭素、酸素あるいは珪素、炭素、窒素を構成原子として含有してなる無機焼結体を意味する。 Specifically, as the Si—C—O based composite, organopolysiloxane capable of highly crosslinking fine particles of silicon, silicon alloy, and silicon oxide (for example, curable organopolysiloxane compositions of addition curing type, condensation curing type, etc.) Etc.), followed by baking in an inert atmosphere at a high temperature to make it inorganic.
As the Si—C—N-based composite, instead of the above-mentioned organopolysiloxane, a highly cross-linkable nitrogen-containing organopolysiloxane (for example, an amino-modified organopolysiloxane composition of addition curing type, condensation curing type, etc.) and / or Or it can obtain by baking and mineralizing similarly using organopolysilazane.
SiN x can be obtained by coating polycarbosilane, followed by firing and mineralization in an ammonia atmosphere.
SiO y can be obtained by coating and curing tetraalkoxysilane or the like, followed by firing and mineralization in the same manner.
The SiC z, coated with tetraalkyl silane, after curing, likewise firing, can be obtained by mineralization.
The Si—C—O based composite and the Si—C—N based composite mean inorganic sintered bodies each containing silicon, carbon, oxygen, or silicon, carbon, and nitrogen as constituent atoms.

この場合、珪素系無機化合物バインダーを形成する有機珪素化合物、その混合物としては特に架橋基を有する反応性シランもしくはシロキサンに代表される有機珪素化合物、又は硬化性ポリシロキサン組成物であることが好ましい。   In this case, the organic silicon compound forming the silicon-based inorganic compound binder, and the mixture thereof is preferably an organic silicon compound represented by a reactive silane or siloxane having a crosslinking group, or a curable polysiloxane composition.

上記有機珪素化合物としては、分子中に珪素原子に結合したアルケニル基等の脂肪族不飽和基、水酸基、水素原子、加水分解性基等の架橋性官能基を２個以上有するものであればよく、２種以上組み合わせてもよい。また、これは直鎖状であっても分岐状であっても環状であってもよく、具体的には下記一般式（１），（２）で表される直鎖状のオルガノポリシロキサン、下記一般式（３）で示される分岐状のオルガノポリシロキサン、下記一般式（４）で表される環状のオルガノポリシロキサン、下記一般式（５）で表されるシランやシリコーンレジン等が例示される。   The organosilicon compound may be any compound having at least two crosslinkable functional groups such as an aliphatic unsaturated group such as an alkenyl group bonded to a silicon atom, a hydroxyl group, a hydrogen atom, and a hydrolyzable group in the molecule. Two or more kinds may be combined. Further, this may be linear, branched or cyclic, and specifically, linear organopolysiloxanes represented by the following general formulas (1) and (2), Examples include branched organopolysiloxanes represented by the following general formula (3), cyclic organopolysiloxanes represented by the following general formula (4), silanes and silicone resins represented by the following general formula (5), and the like. The

これらの有機珪素化合物は、液状であることが好ましいが、シリコーンレジン等で軟化点を有するものであれば固体であってもよい。また、有機珪素化合物を溶解させることができる有機溶剤や非反応性のシリコーンオイルで希釈して使用してもよい。有機溶剤としては、ヘキサン、トルエンやキシレン等が例示され、非反応性のシリコーンオイルとしてはジメチルポリシロキサンオイル等が例示される。   These organosilicon compounds are preferably liquid, but may be solid as long as they have a softening point such as silicone resin. Further, it may be used after diluted with an organic solvent capable of dissolving an organosilicon compound or a non-reactive silicone oil. Examples of the organic solvent include hexane, toluene, and xylene, and examples of the non-reactive silicone oil include dimethylpolysiloxane oil.

（式中、Ｒ1〜Ｒ7は、独立して水素原子、水酸基、加水分解性基、又は１価炭化水素基を示すが、上記式（１）〜（５）の各化合物において、珪素原子に結合する置換基の少なくとも２個は水素原子、水酸基、加水分解性基又は脂肪族不飽和炭化水素基である。ｍ、ｎ、ｋは０〜２，０００、ｐ、ｑは０〜１０であるが、ｐ、ｑは同時に０になることはない。） (Wherein R 1 to R 7 independently represent a hydrogen atom, a hydroxyl group, a hydrolyzable group, or a monovalent hydrocarbon group, but in each compound of the above formulas (1) to (5), a silicon atom At least two of the substituents bonded to are hydrogen atom, hydroxyl group, hydrolyzable group or aliphatic unsaturated hydrocarbon group, m, n and k are 0 to 2,000, p and q are 0 to 10. (However, p and q are not 0 at the same time.)

この場合、加水分解性基としては、アルコキシ基、アルケニロキシ基、アシロキシ基等の炭素数１〜６のものが好ましい。また、１価炭化水素基としては、炭素数１〜１２、特に１〜８のアルキル基、アルケニル基、アルキニル基、アリール基、アラルキル基等が挙げられ、具体的には、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基等のアルキル基、ビニル基、アリル基、ブテニル基、ヘキセニル基、シクロヘキセニル基等のアルケニル基、フェニル基、トリル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基等が例示される。   In this case, the hydrolyzable group is preferably a group having 1 to 6 carbon atoms such as an alkoxy group, an alkenyloxy group, an acyloxy group. Moreover, as a monovalent hydrocarbon group, a C1-C12, especially 1-8 alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, etc. are mentioned, Specifically, a methyl group, an ethyl group, etc. , Alkyl groups such as propyl group, butyl group and hexyl group, alkenyl groups such as vinyl group, allyl group, butenyl group, hexenyl group and cyclohexenyl group, aryl groups such as phenyl group and tolyl group, benzyl group and phenylethyl group And aralkyl groups such as.

また、上記式において、ｍ，ｎ，ｋは０〜２，０００、特に０〜１，０００であり、ｐ，ｑは０〜１０であるが、ｐ，ｑは同時に０になることはなく、ｐ＋ｑが３〜１０であることが好ましい。   In the above formula, m, n, and k are 0 to 2,000, particularly 0 to 1,000, and p and q are 0 to 10, but p and q are not 0 at the same time. It is preferable that p + q is 3-10.

本発明における原料である架橋可能なシラン、シロキサンなどの有機珪素化合物は、一般的なシリコーン製造などで用いるものであれば特に限定しないが、通常、有機シロキサンポリマーのごとき有機珪素系高分子の鎖状ポリマーは、特に非酸化性気流中での加熱によって、その主鎖結合が容易に熱解裂を起こして低分子物（例えば、環状の３−６量体）に分解することにより揮散しやすくなってしまう。これに対して、例えばハイドロシリレーション反応により形成される珪素−炭素結合は、熱に対して強いことから、このようなことによって高度に架橋した場合は低分子化が起こりにくく、起こったとしても高度に架橋しているので揮散しにくいものになる。これによって、焼成過程においても揮散することなく有効に無機物化することができることから、特に上記一般式（１）〜（５）において、分子内にＳｉＨ基を好ましくは２個以上、特に３個以上有するシラン及び／又はシロキサンと、分子内にアルケニル基、アルキニル基といった脂肪族不飽和基を好ましくは２個以上有するシラン及び／又はシロキサンとを使用し、白金、白金化合物等の公知のハイドロシリレーション触媒の存在下にハイドロシリレーション反応して架橋物を形成する付加反応硬化性オルガノポリシロキサン組成物が好ましい。   The organosilicon compounds such as crosslinkable silane and siloxane which are raw materials in the present invention are not particularly limited as long as they are used in general silicone production, etc., but are usually a chain of an organosilicon polymer such as an organosiloxane polymer. The polymer is easily volatilized by heating in a non-oxidizing air current, and its main chain bond easily undergoes thermal cleavage and decomposes into a low molecular weight substance (eg, cyclic 3-6 mer). turn into. On the other hand, for example, silicon-carbon bonds formed by hydrosilylation reaction are strong against heat. Therefore, when this is highly crosslinked, low molecular weight hardly occurs. Since it is highly crosslinked, it is difficult to volatilize. In this way, since it can be effectively converted into an inorganic material without volatilization even in the firing process, in the above general formulas (1) to (5), the number of SiH groups in the molecule is preferably 2 or more, particularly 3 or more. A known hydrosilylation of platinum, platinum compounds, etc., using silane and / or siloxane having silane and / or siloxane having preferably two or more aliphatic unsaturated groups such as alkenyl group and alkynyl group in the molecule An addition reaction curable organopolysiloxane composition that forms a cross-linked product by a hydrosilation reaction in the presence of a catalyst is preferred.

また、分子内に水酸基やアルコキシ基、アシロキシ基等の加水分解性基を有し、触媒反応又は無触媒反応によって縮合し、高度に架橋することが可能なシリコーンレジンを使用することも好ましい。   It is also preferable to use a silicone resin that has a hydrolyzable group such as a hydroxyl group, an alkoxy group, or an acyloxy group in the molecule, and can be condensed by catalytic reaction or non-catalytic reaction and highly crosslinked.

更に、本発明で原料として用いる反応性有機珪素化合物又はその混合物は、下記平均式
ＣhＨiＳｉＯjＮk
（但し、ｈ、ｉ、ｊは正数、ｋは０又は正数である。）
で表され、架橋点が珪素原子４個に対して少なくとも１個有し、かつ（ｈ−ｊ）が０より大きいことが好ましい。なお、Ｎは珪素原子と直接結合又は炭素原子を介して間接的に結合してもよい。 Furthermore, the reactive organosilicon compound or mixture thereof used as a raw material in the present invention has the following average formula C h H i SiO j N k
(However, h, i, and j are positive numbers, and k is 0 or a positive number.)
It is preferable that the number of crosslinking points is at least one for four silicon atoms, and (hj) is greater than zero. N may be bonded directly to the silicon atom or indirectly through a carbon atom.

上記平均式において、ｋ＝０で、ＣhＨiＳｉＯjで示される場合、本発明における炭化珪素の生成反応は下記式により起こり、完全に炭化珪素化する必要はないが、理論的にはｈ−ｊ＝１であることが好ましい。
ＣhＨiＳｉＯj → ＳｉＣ＋ｊＣＯ＋ｉ／２Ｈ2 In the above average equation, when k = 0 and represented by C h H i SiO j , the formation reaction of silicon carbide in the present invention occurs according to the following equation and does not need to be completely silicon carbide, but theoretically It is preferable that h−j = 1.
C h H i SiO j → SiC + jCO + i / 2H 2

しかし、ハイドロシリレーション反応では、若干ロスも見込まれることから、ｈ−ｊが０より大きなシラン、シロキサン又はその混合物、好ましくは０．９〜１．５、更に好ましくは１．０〜１．２となるシラン、シロキサン又はその混合物が好適に用いられる。ｈ−ｊが０以下では原料中の酸素の割合が多くなり、収率の低下及び電気伝導度等の特性が劣ることがあり、逆にｈ−ｊが１．５より大きいと、生成したＣ／Ｓｉ／Ｏ複合材料中に炭素分が多くなり、やはり収率が低下してしまうおそれがある。そのため、ｈ−ｊは０＜ｈ−ｊ≦１．５であることが好ましい。   However, since a slight loss is expected in the hydrosilylation reaction, a silane having a hj greater than 0, siloxane, or a mixture thereof, preferably 0.9 to 1.5, more preferably 1.0 to 1.2. Silane, siloxane or a mixture thereof is preferably used. When hj is 0 or less, the proportion of oxygen in the raw material increases, and the characteristics such as yield reduction and electrical conductivity may be deteriorated. Conversely, when hj is greater than 1.5, the produced C The carbon content in the / Si / O composite material increases, and the yield may also decrease. Therefore, hj is preferably 0 <hj ≦ 1.5.

本発明の珪素複合体粒子において、この粒子中の珪素又は珪素合金含有量は１〜９０質量％、より好ましくは２０〜９０質量％、特に２０〜８０質量％であることが好ましい。この含有量が少なすぎると、単位容量当りの充放電容量（又はエネルギー密度）が低下し、多すぎると、充放電に伴う体積変化の緩和が困難となる。なお、残部は珪素系無機化合物バインダーである。   In the silicon composite particles of the present invention, the silicon or silicon alloy content in the particles is preferably 1 to 90% by mass, more preferably 20 to 90% by mass, and particularly preferably 20 to 80% by mass. If the content is too small, the charge / discharge capacity (or energy density) per unit capacity is reduced, and if it is too large, it is difficult to alleviate the volume change associated with charge / discharge. The balance is a silicon-based inorganic compound binder.

一方、本発明の珪素−炭素複合体粒子において、この粒子中の珪素又は珪素合金含有量は１〜９０質量％とし得るが、２０〜９０質量％、特に４０〜８０質量％であることが好ましい。この含有量が少なすぎると、単位容積当りの充放電容量（又はエネルギー密度）が低下し、多すぎると、サイクル性が低下する。   On the other hand, in the silicon-carbon composite particles of the present invention, the silicon or silicon alloy content in the particles can be 1 to 90% by mass, preferably 20 to 90% by mass, and particularly preferably 40 to 80% by mass. . When the content is too small, the charge / discharge capacity (or energy density) per unit volume is lowered, and when it is too much, the cycle performance is lowered.

また、炭素含有量は、１〜８０質量％、より好ましくは１０〜８０質量％、特に２０〜６０質量％であることが好ましい。珪素系無機化合物バインダー含有量は、前記の珪素又は珪素合金と炭素との合計の残部で、通常１〜９８質量％、好ましくは１０〜８０質量％が好ましい。   The carbon content is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 60% by mass. The silicon-based inorganic compound binder content is usually 1 to 98% by mass, and preferably 10 to 80% by mass, with the remainder of the total of the silicon or silicon alloy and carbon.

更に、珪素複合体粒子、珪素−炭素複合体粒子中の空隙率は、１〜７０体積％、特に５〜５０体積％であることが好ましい。空隙率が少なすぎると、充放電に伴う体積変化の緩和が困難となりサイクル性に劣り、多すぎると、単位容積当りの充放電容量（又はエネルギー密度）が低下する。   Furthermore, the porosity in the silicon composite particles and the silicon-carbon composite particles is preferably 1 to 70% by volume, particularly 5 to 50% by volume. If the porosity is too small, it is difficult to relieve the volume change associated with charge / discharge, resulting in poor cycle performance. If it is too large, the charge / discharge capacity (or energy density) per unit volume is reduced.

また、珪素複合体粒子、珪素−炭素複合体粒子の平均粒径は、リチウムイオン二次電池負極材として用いた場合、負極膜としての成膜性及びサイクル性向上の点から、０．５〜３０μｍ、より好ましくは１〜３０μｍ、特に５〜２０μｍであることが好ましい。この場合、平均粒径は、レーザー光回折法による粒度分布測定における質量平均値Ｄ50（即ち、累積質量が５０％となるときの粒子径又はメジアン径）として測定した値である。 In addition, the average particle size of the silicon composite particles and silicon-carbon composite particles is 0.5 to 0.5 when used as a negative electrode material for a lithium ion secondary battery from the viewpoint of improving film formability and cycle performance as a negative electrode film. It is preferably 30 μm, more preferably 1 to 30 μm, particularly preferably 5 to 20 μm. In this case, the average particle diameter is a value measured as a mass average value D 50 (that is, a particle diameter or a median diameter when the cumulative mass is 50%) in the particle size distribution measurement by the laser light diffraction method.

本発明の珪素複合体粒子、珪素−炭素複合体粒子は、その表面がカーボンで被覆されていてもよい。ここで、本発明における珪素複合体粒子あるいは珪素−炭素複合体粒子に対する被覆（蒸着）炭素量は、上記珪素複合体粒子あるいは珪素−炭素複合体粒子に対し、１〜５０質量％が好ましい。特に、５〜４０質量％が好ましく、更に５〜３０質量％が好ましい。被覆（蒸着）炭素量が１質量％未満では、当該珪素又は珪素−炭素複合体粒子を単独で負極活物質として用いた場合、負極膜の導電性が不足し、リチウムイオン二次電池とした場合のサイクル特性など電池特性の発現が十分ではない場合があり、５０質量％を超えると、炭素の割合が多くなりすぎ、負極容量が減少してしまい、効果が減少してしまう。   The surface of the silicon composite particles and silicon-carbon composite particles of the present invention may be coated with carbon. Here, the coating (vapor deposition) carbon amount with respect to the silicon composite particles or silicon-carbon composite particles in the present invention is preferably 1 to 50% by mass with respect to the silicon composite particles or silicon-carbon composite particles. In particular, 5-40 mass% is preferable and 5-30 mass% is more preferable. When the amount of coated (vapor-deposited) carbon is less than 1% by mass, when the silicon or silicon-carbon composite particles are used alone as the negative electrode active material, the negative electrode film has insufficient conductivity, resulting in a lithium ion secondary battery. In some cases, the battery characteristics such as the cycle characteristics are not sufficiently exhibited. When the amount exceeds 50% by mass, the proportion of carbon is excessively increased, the negative electrode capacity is decreased, and the effect is decreased.

特に単独で負極活物質として使用される場合、珪素複合体粒子及び珪素−炭素複合体の電気導電率は１×１０-6Ｓ／ｍ以上、特に１×１０-4Ｓ／ｍ以上が望ましい。電気伝導率が１×１０-6Ｓ／ｍより小さいと電極の導電性が小さく、リチウムイオン二次電池用負極材として用いた場合にサイクル性が低下するおそれがある。なお、ここでいう、電気伝導率とは４端子を持つ円筒状のセル内に被測定粉末を充填し、この被測定粉末に電流を流した時の電圧降下を測定することで求めた値である。 In particular, when used alone as the negative electrode active material, the electrical conductivity of the silicon composite particles and the silicon-carbon composite is preferably 1 × 10 −6 S / m or more, and more preferably 1 × 10 −4 S / m or more. When the electric conductivity is less than 1 × 10 −6 S / m, the electrode has low conductivity, and when used as a negative electrode material for a lithium ion secondary battery, the cycle performance may be lowered. Here, the electric conductivity is a value obtained by filling a powder to be measured in a cylindrical cell having four terminals and measuring a voltage drop when a current is passed through the powder to be measured. is there.

次に、本発明における珪素複合体粒子、珪素−炭素複合体粒子の製造方法について説明する。
本発明の珪素複合体粒子、珪素−炭素複合体粒子は、珪素又は珪素系合金の微粒子又は該微粒子と炭素微粒子が珪素系化合物に分散し、かつその内部に空隙を有する構造を有する焼結体粒子であって、特に１〜３０μｍ程度の平均粒子径を有するものであれば、その製造方法は特に限定されるものではないが、例えば下記Ｉ〜ＩＩの方法を好適に採用することができる。
Ｉ：珪素や珪素合金塊を機械的な粉砕によって粉砕するなどの方法で得られた、好ましくは１００ｎｍ〜１０μｍ、より好ましくは１００ｎｍ〜７μｍ、更に好ましくは１〜５μｍに分級した珪素粉、珪素系合金粉、酸化珪素粉、又はこれと好ましくは１００ｎｍ〜２０μｍ、より好ましくは１〜２０μｍ、更に好ましくは３〜１０μｍに分級された球状又は鱗片状炭素粉との混合物に、上述した有機珪素化合物又はその混合物、特に白金触媒、ビニルシロキサン、水素シロキサンからなる付加反応硬化型オルガノポリシロキサン組成物を添加し、よく混合後、３００℃以下の温度でプレキュアする。この場合、プレキュア温度の下限は特に制限されないが、４０℃以上であることが好ましい。この場合、必要に応じて有機溶剤を添加してよく均一になるようにする。その後、不活性雰囲気下で５００〜１，４００℃、特に６００〜１，４００℃、好ましくは７５０〜１，３００℃、より好ましくは９００〜１，２００℃の温度域で熱処理することにより、内部に空隙を有するＳｉ−Ｃ−Ｏ系コンポジット、Ｓｉ−Ｃ−Ｎ系コンポジット、ＳｉＮx、ＳｉＯy、ＳｉＣz等をバインダーとする珪素複合体又は珪素−炭素複合体の凝集物が得られる。この内部のモデルを図１，２に、実際のＳＥＭ観察例を図４〜６に示し、図７はＲＥＭ観察像（即ち、反射電子検出器（Ｂａｃｋｓｃａｔｔｅｒｅｄ Ｅｌｅｃｔｒｏｎ Ｄｅｔｅｃｔｏｒ）で検出した反射電子を組成像（ＣＯＭＰＯ Ｉｍａｇｅ）に変換した反射電子像（ＢＥＩ：Ｂａｃｋｓｃａｔｔｅｒｅｄ Ｅｌｅｃｔｒｏｎ Ｉｍａｇｅ））を示す（なお、図４は珪素複合体、図５〜７は珪素−炭素複合体である）。この後、所定の粒度に粉砕、分級して珪素複合体を得るが、粉砕方法は特に問わない。なお、プレキュア時の雰囲気は特に制限されない。また、不活性ガス雰囲気は、窒素雰囲気、アルゴン雰囲気等の非酸化性雰囲気とすることができる。 Next, a method for producing silicon composite particles and silicon-carbon composite particles in the present invention will be described.
The silicon composite particles and silicon-carbon composite particles of the present invention are sintered bodies having a structure in which fine particles of silicon or a silicon-based alloy or fine particles and carbon fine particles are dispersed in a silicon-based compound and have voids therein. The method for producing the particles is not particularly limited as long as the particles have an average particle size of about 1 to 30 μm. For example, the following methods I to II can be suitably employed.
I: Silicon powder obtained by a method such as pulverizing silicon or a silicon alloy lump by mechanical pulverization, preferably 100 nm to 10 μm, more preferably 100 nm to 7 μm, still more preferably 1 to 5 μm, The above-mentioned organosilicon compound or a mixture of an alloy powder, silicon oxide powder, or a spherical or scaly carbon powder classified to 100 nm to 20 μm, more preferably 1 to 20 μm, and even more preferably 3 to 10 μm. The mixture, particularly an addition reaction curable organopolysiloxane composition composed of a platinum catalyst, vinyl siloxane, and hydrogen siloxane, is added and thoroughly mixed, and then precured at a temperature of 300 ° C. or lower. In this case, the lower limit of the precure temperature is not particularly limited, but is preferably 40 ° C. or higher. In this case, if necessary, an organic solvent may be added so as to be uniform. Thereafter, heat treatment is performed in a temperature range of 500 to 1,400 ° C., particularly 600 to 1,400 ° C., preferably 750 to 1,300 ° C., more preferably 900 to 1,200 ° C. in an inert atmosphere. An agglomerate of a silicon composite or a silicon-carbon composite containing a Si—C—O composite, Si—C—N composite, SiN x , SiO y , SiC z or the like having voids in the gap is obtained. The internal model is shown in FIGS. 1 and 2, and actual SEM observation examples are shown in FIGS. 4 to 6. FIG. 7 is a composition image of the REM observation image (that is, the reflected electrons detected by the backscattered electron detector). FIG. 4 shows a backscattered electron image (BEI) converted into (COMPO Image) (FIG. 4 is a silicon composite, and FIGS. 5 to 7 are silicon-carbon composites). Thereafter, the silicon composite is obtained by pulverization and classification to a predetermined particle size, but the pulverization method is not particularly limited. The atmosphere during precure is not particularly limited. The inert gas atmosphere can be a non-oxidizing atmosphere such as a nitrogen atmosphere or an argon atmosphere.

この場合、珪素又は珪素合金微粒子と有機珪素化合物又はその混合物との密着性を改良するために、珪素又は珪素合金微粒子表面を下記式で表されるシランカップリング剤、その（部分）加水分解縮合物、オルガノポリシラザンなどのシリル化剤、シリコーンレジンから選ばれる１種又は２種以上の有機珪素系表面処理剤などで処理することは有効である。   In this case, in order to improve the adhesion between the silicon or silicon alloy fine particles and the organosilicon compound or a mixture thereof, the surface of the silicon or silicon alloy fine particles is represented by the following formula, and (partial) hydrolysis condensation thereof It is effective to treat with a silylating agent such as an organic polysilazane, or one or more organic silicon surface treating agents selected from silicone resins.

（但し、Ｒは一価の有機基、Ｙは１価の加水分解性基又は水酸基、Ｚは２価の加水分解性基、ａは１〜４の整数、ｂは０．８〜３、好ましくは１〜３の正数である。）
Ｒ'e（Ｒ''Ｏ）fＳｉＯ(4-e-f)/2 （８）
（但し、Ｒ'は水素原子又は炭素数が１〜１０の置換もしくは非置換の一価炭化水素基、Ｒ''は水素原子又は炭素数が１〜６の置換もしくは非置換の一価炭化水素基であり、ｅ，ｆはそれぞれ０≦ｅ≦２．５、０．０１≦ｆ≦３、０．５≦ｅ＋ｆ≦３を満足する０又は正数である。） (However, R is a monovalent organic group, Y is a monovalent hydrolyzable group or hydroxyl group, Z is a divalent hydrolyzable group, a is an integer of 1 to 4, and b is 0.8 to 3, preferably Is a positive number from 1 to 3.)
R ′ e (R ″ O) f SiO (4-ef) / 2 (8)
(However, R ′ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ″ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms. E and f are 0 or a positive number satisfying 0 ≦ e ≦ 2.5, 0.01 ≦ f ≦ 3, and 0.5 ≦ e + f ≦ 3, respectively.)

ここで、Ｒとしては、炭素数１〜１２、特に１〜１０のアルキル基、シクロアルキル基、アルケニル基、アリール基、アラルキル基などの非置換一価炭化水素基や、これらの基の水素原子の一部又は全部をハロゲン原子（塩素、フッ素、臭素原子等）、シアノ基、オキシエチレン基等のオキシアルキレン基、ポリオキシエチレン基等のポリオキシアルキレン基、（メタ）アクリル基、（メタ）アクリロキシ基、アクリロイル基、メタクリロイル基、メルカプト基、アミノ基、アミド基、ウレイド基、エポキシ基などの官能基で置換した置換一価炭化水素基、これら非置換又は置換一価炭化水素基において、酸素原子、ＮＨ基、ＮＣＨ3基、ＮＣ6Ｈ5基、Ｃ6Ｈ5ＮＨ−基、Ｈ2ＮＣＨ2ＣＨ2ＮＨ−基などが介在した基を挙げることができる。 Here, R is an unsubstituted monovalent hydrocarbon group such as an alkyl group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group, or a hydrogen atom of these groups. A part or all of halogen atoms (chlorine, fluorine, bromine atoms, etc.), cyano groups, oxyalkylene groups such as oxyethylene groups, polyoxyalkylene groups such as polyoxyethylene groups, (meth) acryl groups, (meth) In the substituted monovalent hydrocarbon group substituted by a functional group such as acryloxy group, acryloyl group, methacryloyl group, mercapto group, amino group, amide group, ureido group, epoxy group, etc., in these unsubstituted or substituted monovalent hydrocarbon groups, oxygen A group in which an atom, NH group, NCH 3 group, NC 6 H 5 group, C 6 H 5 NH— group, H 2 NCH 2 CH 2 NH— group or the like is interposed .

Ｒの具体例としては、ＣＨ3−、ＣＨ3ＣＨ2−、ＣＨ3ＣＨ2ＣＨ2−などのアルキル基、ＣＨ2＝ＣＨ−、ＣＨ2＝ＣＨＣＨ2−、ＣＨ2＝Ｃ（ＣＨ3）−などのアルケニル基、Ｃ6Ｈ5−などのアリール基、ＣｌＣＨ2−、ＣｌＣＨ2ＣＨ2ＣＨ2−、ＣＦ3ＣＨ2ＣＨ2−、（ＣＮ）ＣＨ2ＣＨ2−、ＣＨ3−（ＣＨ2ＣＨ2Ｏ）3−ＣＨ2ＣＨ2ＣＨ2−、ＣＨ2（Ｏ）ＣＨＣＨ2ＯＣＨ2ＣＨ2ＣＨ2−（但し、ＣＨ2（Ｏ）ＣＨＣＨ2はグリシジル基を示す）、ＣＨ2＝ＣＨＣＯＯＣＨ2−、
ＨＳＣＨ2ＣＨ2ＣＨ2−、ＮＨ2ＣＨ2ＣＨ2ＣＨ2−、ＮＨ2ＣＨ2ＣＨ2ＮＨＣＨ2ＣＨ2ＣＨ2−、ＮＨ2ＣＯＮＨＣＨ2ＣＨ2ＣＨ2−などが挙げられる。好ましいＲとしては、γ−グリシジルオキシプロピル基、β−（３，４−エポキシシクロヘキシル）エチル基、γ−アミノプロピル基、γ−シアノプロピル基、γ−アクリルオキシプロピル基、γ−メタクリルオキシプロピル基、γ−ウレイドプロピル基などである。 Specific examples of R include alkyl groups such as CH 3 —, CH 3 CH 2 —, CH 3 CH 2 CH 2 —, CH 2 ═CH—, CH 2 ═CHCH 2 —, CH 2 ═C (CH 3 ). An alkenyl group such as —, an aryl group such as C 6 H 5 —, ClCH 2 —, ClCH 2 CH 2 CH 2 —, CF 3 CH 2 CH 2 —, (CN) CH 2 CH 2 —, CH 3 — (CH 2 CH 2 O) 3 —CH 2 CH 2 CH 2 —, CH 2 (O) CHCH 2 OCH 2 CH 2 CH 2 — (wherein CH 2 (O) CHCH 2 represents a glycidyl group), CH 2 = CHCOOCH 2 −,
HSCH 2 CH 2 CH 2 —, NH 2 CH 2 CH 2 CH 2 —, NH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2 —, NH 2 CONHCH 2 CH 2 CH 2 — and the like can be mentioned. Preferred R is γ-glycidyloxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ-aminopropyl group, γ-cyanopropyl group, γ-acryloxypropyl group, γ-methacryloxypropyl group. , Γ-ureidopropyl group and the like.

Ｙの１価の加水分解性基としては、−ＯＣＨ3、−ＯＣＨ2ＣＨ3などのアルコキシ基、−ＮＨ2、−ＮＨ−、−Ｎ＝、−Ｎ（ＣＨ3）2などのアミノ基、−Ｃｌ、−ＯＮ＝Ｃ（ＣＨ3）ＣＨ2ＣＨ3などのオキシミノ基、−ＯＮ（ＣＨ3）2などのアミノオキシ基、−ＯＣＯＣＨ3などのカルボキシル基、−ＯＣ（ＣＨ3）＝ＣＨ2などのアルケニルオキシ基、−ＣＨ（ＣＨ3）−ＣＯＯＣＨ3、−Ｃ（ＣＨ3）2−ＣＯＯＣＨ3などが挙げられる。Ｙは全て同一の基であっても異なる基であってもよい。好ましいＹとしては、メトキシ基、エトキシ基等のアルコキシ基、イソプロペニルオキシ基等のアルケニルオキシ基等である。また、２価の加水分解性基であるＺとしては、イミド残基（−ＮＨ−）、非置換又は置換のアセトアミド残基、ウレア残基、カーバメート残基、サルファメート残基などである。 Examples of the monovalent hydrolyzable group for Y include alkoxy groups such as —OCH 3 and —OCH 2 CH 3 , amino groups such as —NH 2 , —NH—, —N═, and —N (CH 3 ) 2 ; -Cl, -ON = C (CH 3 ) CH oximino group such as 2 CH 3, amino group such as -ON (CH 3) 2, carboxyl group, such as -OCOCH 3, -OC (CH 3) = CH 2 alkenyloxy groups such as, -CH (CH 3) -COOCH 3 , like -C (CH 3) 2 -COOCH 3 . Y may be all the same group or different groups. Preferred Y is an alkoxy group such as a methoxy group or an ethoxy group, an alkenyloxy group such as an isopropenyloxy group, or the like. Z, which is a divalent hydrolyzable group, includes an imide residue (—NH—), an unsubstituted or substituted acetamido residue, a urea residue, a carbamate residue, a sulfamate residue, and the like.

ａは１〜４の整数、好ましくは３又は４である。ｂは０．８〜３、好ましくは１〜３の正数である。   a is an integer of 1 to 4, preferably 3 or 4. b is a positive number of 0.8 to 3, preferably 1 to 3.

シランカップリング剤の具体例としては、メチルトリメトキシシラン、テトラエトキシシラン、ビニルトリメトキシシラン、メチルビニルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−シアノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−メタクリルオキシプロピルトリメトキシシラン、γ−グリシジルオキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−ウレイドプロピルトリメトキシシランなどのテトラアルコキシシラン、オルガノトリアルコキシシラン、ジオルガノジアルコキシシラン等のアルコキシシラン類が挙げられる。シランカップリング剤は単独でもよいし、２種類以上を混合してもよい。又はその加水分解縮合物及び／又はその部分加水分解縮合物であってもよい。   Specific examples of the silane coupling agent include methyltrimethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, methylvinyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-cyanopropyltri Methoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri Examples include tetraalkoxysilanes such as methoxysilane and γ-ureidopropyltrimethoxysilane, and alkoxysilanes such as organotrialkoxysilane and diorganodialkoxysilane. A silane coupling agent may be individual and may mix two or more types. Or the hydrolysis condensate and / or the partial hydrolysis condensate thereof may be sufficient.

また、上記一般式（７）のシリル化剤の具体例としては、ヘキサメチルジシラザン、ジビニルテトラメチルジシラザン、テトラビニルジメチルジシラザン、オクタメチルトリシラザン等のオルガノ（ポリ）シラザン、Ｎ，Ｏ−ビス（トリメチルシリル）アセトアミド、Ｎ，Ｏ−ビス（トリメチルシリル）カーバメート、Ｎ，Ｏ−ビス（トリメチルシリル）サルファメート、Ｎ，Ｏ−ビス（トリメチルシリル）トリフロロアセトアミド、Ｎ，Ｎ’−ビス（トリメチルシリル）ウレア等が挙げられるが、特にジビニルテトラメチルジシラザンが好適である。   Specific examples of the silylating agent represented by the general formula (7) include organo (poly) silazanes such as hexamethyldisilazane, divinyltetramethyldisilazane, tetravinyldimethyldisilazane, octamethyltrisilazane, N, O, and the like. -Bis (trimethylsilyl) acetamide, N, O-bis (trimethylsilyl) carbamate, N, O-bis (trimethylsilyl) sulfamate, N, O-bis (trimethylsilyl) trifluoroacetamide, N, N'-bis (trimethylsilyl) urea Among them, divinyltetramethyldisilazane is particularly preferable.

一方、上記一般式（８）において、Ｒ’、Ｒ”は上記Ｒのうち炭素数が上記の定義に合致するものが挙げられ、特にアルキル、シクロアルキル、アルケニル、アリール基等が好ましい。
上記一般式（８）のシリコーンレジンとしては、例えば、前記したシランカップリング剤として例示したテトラエトキシシラン、ビニルトリメトキシシラン、メチルビニルジメトキシシラン等のテトラアルコキシシラン、オルガノトリアルコキシシラン、ジオルガノジアルコキシシラン等の１分子中に２〜４個のアルコキシ基を有するアルコキシシランを部分加水分解縮合して得られる、残基アルコキシ基を１分子中に少なくとも１個、好ましくは２個以上有する、通常珪素原子数２〜５０個、好ましくは２〜３０個程度のオルガノシロキサンオリゴマー等が挙げられる。 On the other hand, in the general formula (8), examples of R ′ and R ″ include those in which the number of carbon atoms in the R matches the above definition, and alkyl, cycloalkyl, alkenyl, aryl groups and the like are particularly preferable.
Examples of the silicone resin of the general formula (8) include tetraalkoxysilanes such as tetraethoxysilane, vinyltrimethoxysilane, and methylvinyldimethoxysilane exemplified as the silane coupling agent, organotrialkoxysilane, and diorganodi. It has at least one, preferably two or more residue alkoxy groups in one molecule, obtained by partial hydrolysis and condensation of alkoxysilane having 2 to 4 alkoxy groups in one molecule such as alkoxysilane. Examples include organosiloxane oligomers having 2 to 50 silicon atoms, preferably about 2 to 30 silicon atoms.

なお、上記表面処理剤の使用量は、珪素又は珪素合金微粒子の質量に対して、通常０．１〜５０質量％、好ましくは０．５〜３０質量％、より好ましくは１〜５質量％程度とすることができる。   In addition, the usage-amount of the said surface treating agent is 0.1-50 mass% normally with respect to the mass of silicon or silicon alloy fine particles, Preferably it is 0.5-30 mass%, More preferably, it is about 1-5 mass%. It can be.

ＩＩ：Ｉによって得た珪素複合体粒子あるいは珪素−炭素複合体粒子を、好ましくは０．１〜５０μｍの粒度まで粉砕したものを、少なくとも有機物ガス及び／又は蒸気を含む非
酸化性雰囲気下、８００〜１，４００℃、好ましくは９００〜１，３００℃、より好ましくは１，０００〜１，２００℃の温度域で熱処理して表面を化学蒸着する方法。 II: The silicon composite particles or silicon-carbon composite particles obtained by I, preferably pulverized to a particle size of 0.1 to 50 μm, in a non-oxidizing atmosphere containing at least an organic gas and / or steam, 800 A method of chemically vapor-depositing the surface by heat treatment in a temperature range of ˜1,400 ° C., preferably 900˜1,300 ° C., more preferably 1,000˜1,200 ° C.

上記Ｉの方法に関し、珪素、珪素合金又は酸化珪素粉と、白金触媒などのハイドロシリレーション触媒を含む反応性のビニルシロキサンと水素シロキサンを混合した付加反応硬化型オルガノポリシロキサン組成物を混合した後、３００℃以下の温度で、プレキュアをせずに、高温の焼成温度まで温度を上昇させた場合、低分子シロキサンへのシロキサンのクラッキングなどが先行して、ロス分が多くなってしまう。また、不活性雰囲気下での焼成温度が６００℃、特に５００℃より低いと、無機化が不十分で電池特性的に問題が生じる。一方、１，４００℃を超えて高すぎた場合、珪素の溶融や凝集が起こり、また酸化珪素を用いた場合、その不均化が進みすぎることによるサイクル低下を招く。   After mixing an addition reaction curable organopolysiloxane composition in which silicon, a silicon alloy or silicon oxide powder and a reactive vinyl siloxane containing a hydrosilation catalyst such as a platinum catalyst and hydrogen siloxane are mixed. When the temperature is raised to a high firing temperature without pre-curing at a temperature of 300 ° C. or lower, siloxane cracking to a low-molecular siloxane precedes, resulting in an increase in loss. On the other hand, if the firing temperature in an inert atmosphere is lower than 600 ° C., particularly less than 500 ° C., mineralization is insufficient and a problem occurs in battery characteristics. On the other hand, if it exceeds 1,400 ° C. and is too high, melting and aggregation of silicon occur, and if silicon oxide is used, cycle disproportionation due to excessive disproportionation is caused.

一方、上記ＩＩの方法に関し、８００℃より低い温度の場合、炭化乃至は無機化が不十分となり、初期効率やサイクル性の低下を招く。高温すぎた場合は、上記と同様のリチウムイオン二次電池において電池特性的な問題が発生する。   On the other hand, in the case of the method II, when the temperature is lower than 800 ° C., carbonization or mineralization becomes insufficient, leading to a decrease in initial efficiency and cycleability. When the temperature is too high, battery characteristic problems occur in the same lithium ion secondary battery as described above.

このように、好ましくは熱ＣＶＤ（８００℃以上での化学蒸着処理）を施すことによりカーボン膜を作製するが、熱ＣＶＤの時間は、カーボン量との関係で、適宜設定される。この処理において粒子が凝集する場合があるが、この凝集物をボールミル等で解砕する。また、場合によっては、再度同様に熱ＣＶＤを繰り返し行う。   As described above, the carbon film is preferably formed by performing thermal CVD (chemical vapor deposition at 800 ° C. or higher), and the thermal CVD time is appropriately set in relation to the amount of carbon. In this treatment, particles may be aggregated, and the aggregate is crushed with a ball mill or the like. In some cases, thermal CVD is repeated again in the same manner.

本発明における有機物ガスを発生する原料として用いられる有機物としては、特に非酸化性雰囲気下において、上記熱処理温度で熱分解して炭素（黒鉛）を生成し得るものが選択され、例えばメタン、エタン、エチレン、アセチレン、プロパン、ブタン、ブテン、ペンタン、イソブタン、ヘキサン等の炭化水素の単独もしくは混合物、ベンゼン、トルエン、キシレン、スチレン、エチルベンゼン、ジフェニルメタン、ナフタレン、フェノール、クレゾール、ニトロベンゼン、クロルベンゼン、インデン、クマロン、ピリジン、アントラセン、フェナントレン等の１環乃至３環の芳香族炭化水素もしくはこれらの混合物が挙げられる。また、タール蒸留工程で得られるガス軽油、クレオソート油、アントラセン油、ナフサ分解タール油も単独もしくは混合物として用いることができる。   As an organic substance used as a raw material for generating an organic gas in the present invention, an organic substance that can be thermally decomposed at the above heat treatment temperature to generate carbon (graphite) is selected, particularly in a non-oxidizing atmosphere. For example, methane, ethane, A single or mixture of hydrocarbons such as ethylene, acetylene, propane, butane, butene, pentane, isobutane, hexane, benzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene, coumarone , Pyridine, anthracene, phenanthrene, and the like, and monocyclic to tricyclic aromatic hydrocarbons or a mixture thereof. Further, gas light oil, creosote oil, anthracene oil, and naphtha cracked tar oil obtained in the tar distillation step can be used alone or as a mixture.

なお、上記熱ＣＶＤ（熱化学蒸着処理）は、非酸化性雰囲気において、加熱機構を有する反応装置を用いればよく、特に限定されず、連続法、回分法での処理が可能で、具体的には流動層反応炉、回転炉、竪型移動層反応炉、トンネル炉、バッチ炉、ロータリーキルン等をその目的に応じ適宜選択することができる。この場合、（処理）ガスとしては、上記有機物ガス単独あるいは有機物ガスとＡｒ、Ｈｅ、Ｈ2、Ｎ2等の非酸化性ガスの混合ガスを用いることができる。 The thermal CVD (thermochemical vapor deposition process) is not particularly limited as long as a reaction apparatus having a heating mechanism is used in a non-oxidizing atmosphere, and can be processed by a continuous process or a batch process. The fluidized bed reactor, rotary furnace, vertical moving bed reactor, tunnel furnace, batch furnace, rotary kiln and the like can be appropriately selected according to the purpose. In this case, as the (treatment) gas, the organic gas alone or a mixed gas of the organic gas and a non-oxidizing gas such as Ar, He, H 2 or N 2 can be used.

本発明で得られた珪素又は珪素−炭素複合体粒子は、これを負極材（負極活物質）として用い、高容量でかつサイクル特性の優れた非水電解質二次電池、特に、リチウムイオン二次電池を製造することができる。   The silicon or silicon-carbon composite particles obtained in the present invention are used as a negative electrode material (negative electrode active material), and have a high capacity and excellent cycle characteristics, particularly a lithium ion secondary battery. A battery can be manufactured.

この場合、得られたリチウムイオン二次電池は、上記珪素又は珪素−炭素複合体粒子を用いた負極活物質を用いる点に特徴を有し、その他の正極、負極、電解質、セパレータなどの材料及び電池形状などは限定されない。例えば、正極活物質としてはＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4、Ｖ2Ｏ6、ＭｎＯ2、ＴｉＳ2、ＭｏＳ2などの遷移金属の酸化物及びカルコゲン化合物などが用いられる。電解質としては、例えば、過塩素酸リチウムなどのリチウム塩を含む非水溶液が用いられ、非水溶媒としてはプロピレンカーボネート、エチレンカーボネート、ジメトキシエタン、γ−ブチロラクトン、２−メチルテトラヒドロフランなどの単体又は２種類以上を組み合わせて用いられる。また、それ以外の種々の非水系電解質や固体電解質も使用できる。 In this case, the obtained lithium ion secondary battery is characterized in that a negative electrode active material using the above silicon or silicon-carbon composite particles is used, and other positive electrode, negative electrode, electrolyte, separator and other materials and The battery shape and the like are not limited. For example, as the positive electrode active material, oxides of transition metals such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , V 2 O 6 , MnO 2 , TiS 2 , and MoS 2 , chalcogen compounds, and the like are used. As the electrolyte, for example, a non-aqueous solution containing a lithium salt such as lithium perchlorate is used, and as the non-aqueous solvent, propylene carbonate, ethylene carbonate, dimethoxyethane, γ-butyrolactone, 2-methyltetrahydrofuran or the like alone or in two types The above is used in combination. Various other non-aqueous electrolytes and solid electrolytes can also be used.

なお、上記珪素複合体粒子又は珪素−炭素複合体粒子を用いて負極を作製する場合、珪素複合体粒子又は珪素−炭素複合体粒子に黒鉛等の導電剤を添加することができる。この場合においても導電剤の種類は特に限定されず、構成された電池において、分解や変質を起こさない電子伝導性の材料であればよく、具体的にはＡｌ，Ｔｉ，Ｆｅ，Ｎｉ，Ｃｕ，Ｚｎ，Ａｇ，Ｓｎ，Ｓｉ等の金属粉末や金属繊維、又は天然黒鉛、人造黒鉛、各種のコークス粉末、メソフェーズ炭素、気相成長炭素繊維、ピッチ系炭素繊維、ＰＡＮ系炭素繊維、各種の樹脂焼成体等の黒鉛を用いることができる。   When a negative electrode is produced using the silicon composite particles or silicon-carbon composite particles, a conductive agent such as graphite can be added to the silicon composite particles or silicon-carbon composite particles. Also in this case, the kind of the conductive agent is not particularly limited, and any electronic conductive material that does not cause decomposition or alteration in the constituted battery may be used. Specifically, Al, Ti, Fe, Ni, Cu, Metal powder and metal fiber such as Zn, Ag, Sn, Si, or natural graphite, artificial graphite, various coke powders, mesophase carbon, vapor-grown carbon fiber, pitch-based carbon fiber, PAN-based carbon fiber, various resin firing Graphite such as a body can be used.

ここで、珪素複合体粒子を用いる場合、同様に導電剤は熱ＣＶＤによってカーボンコートした珪素複合体粒子では必ずしも必要としないが、未処理のものでは、導電剤の添加量は、珪素−炭素複合体粒子と導電剤の混合物中１０〜７０質量％が好ましく、特に２０〜５０質量％、とりわけ２０〜４０質量％が好ましい。１０質量％未満だと充放電に伴う膨張・収縮に耐えられなくなる場合があり、７０質量％を超えると充放電容量が小さくなる場合がある。
一方、珪素−炭素複合体粒子の場合、同様に導電剤は熱ＣＶＤによってカーボンコートしたものでは、必ずしも必要としないが、未処理のものでは、導電剤の添加量は、珪素−炭素複合体粒子と導電剤の混合物中１０〜７０質量％が好ましく、特に２０〜５０質量％、とりわけ２０〜４０質量％が好ましい。１０質量％未満だと充放電に伴う膨張・収縮に耐えられなくなる場合があり、７０質量％を超えると充放電容量が小さくなる場合がある。 Here, when using silicon composite particles, similarly, the conductive agent is not necessarily required for silicon composite particles coated with carbon by thermal CVD, but in the case of untreated one, the amount of conductive agent added is silicon-carbon composite. 10-70 mass% is preferable in the mixture of a body particle and a electrically conductive agent, 20-50 mass% is especially preferable, and especially 20-40 mass% is preferable. If it is less than 10% by mass, it may not be able to withstand expansion / contraction associated with charge / discharge, and if it exceeds 70% by mass, the charge / discharge capacity may be reduced.
On the other hand, in the case of silicon-carbon composite particles, similarly, the conductive agent is not necessarily required if it is carbon-coated by thermal CVD, but in the case of an untreated one, the amount of conductive agent added is silicon-carbon composite particles. Is preferably 10 to 70% by mass, particularly 20 to 50% by mass, especially 20 to 40% by mass in the mixture of the conductive agent and the conductive agent. If it is less than 10% by mass, it may not be able to withstand expansion / contraction associated with charge / discharge, and if it exceeds 70% by mass, the charge / discharge capacity may be reduced.

以下、実施例及び比較例を挙げて本発明を具体的に説明するが、本発明は下記実施例に限定されるものではない。なお、下記例で％は質量％、部は質量部を示し、ｇｒはグラムを示す。   EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to the following Example. In the following examples,% represents mass%, part represents mass part, and gr represents gram.

［実施例１］
化学用金属珪素（豪州ＳＩＭＣＯＡ社製低Ａｌ品；Ａｌ：０．０５％，Ｆｅ：０．２１％，Ｃａ：０．００３％）を、ジョークラッシャーで粗砕し、更にヘキサンを分散媒としてボールミル及びビーズミルで平均粒径約１μｍの微粒子にまで粉砕した。得られた懸濁物をろ過し、窒素雰囲気下で脱溶剤後、日清エンジニアリング（株）製空気式精密分級機で粗粒部分をカットし、平均粒径が約０．８μｍの粉末を得た。この珪素微粉末１００ｇｒを、テトラメチルテトラビニルシクロテトラシロキサン〔信越化学工業（株）製ＬＳ−８６７０〕１２ｇｒ、メチル水素シロキサン〔信越化学工業（株）製ＫＦ−９９〕８ｇｒ及び塩化白金酸触媒〔塩化白金酸１％溶液〕０．１ｇｒからなる硬化性シロキサン組成物とヘキサン３０ｍｌの混合物に添加し、パテ状の状態でよく混合した。その後、６０℃で脱溶剤・プレキュアした。
塊状のまま、蓋付のアルミナ製容器に入れて、雰囲気コントロール可能な温度プログラム付マッフル炉で窒素雰囲気下にて、３００℃×２時間＋１，０００℃×３時間という温度条件で焼成を行った。十分冷却後、クリアランスを２０μｍに設定した粉砕機（マスコロイダー）で粉砕し、平均粒径約１０μｍの珪素複合体（ゼロ価の珪素微粒子含有量は８６質量％であり、空隙率は比重測定より３０容量％であった（以下同様）。）を得た。 [Example 1]
Metallic silicon for chemical use (low aluminum product manufactured by SIMCOA, Australia; Al: 0.05%, Fe: 0.21%, Ca: 0.003%) is coarsely crushed with a jaw crusher, and then ball mill using hexane as a dispersion medium And it grind | pulverized to the microparticles | fine-particles with an average particle diameter of about 1 micrometer with the bead mill. The obtained suspension was filtered, and after removing the solvent under a nitrogen atmosphere, the coarse particles were cut with an air precision classifier manufactured by Nissin Engineering Co., Ltd. to obtain a powder having an average particle size of about 0.8 μm. It was. 100 g of this silicon fine powder was added to 12 g of tetramethyltetravinylcyclotetrasiloxane [LS-8670 manufactured by Shin-Etsu Chemical Co., Ltd.], 8 gr of methylhydrogensiloxane [KF-99 manufactured by Shin-Etsu Chemical Co., Ltd.] and a chloroplatinic acid catalyst [ Chloroplatinic acid 1% solution] was added to a mixture of a curable siloxane composition consisting of 0.1 gr and 30 ml of hexane and mixed well in a putty-like state. Thereafter, the solvent was removed and precured at 60 ° C.
As a lump, it was placed in an alumina container with a lid and baked under a nitrogen atmosphere in a muffle furnace with a temperature program capable of controlling the atmosphere under a temperature condition of 300 ° C. × 2 hours + 1,000 ° C. × 3 hours. . After cooling sufficiently, the mixture is pulverized by a pulverizer (mass colloider) with a clearance set to 20 μm, and a silicon composite having an average particle diameter of about 10 μm (zero-valent silicon fine particle content is 86% by mass, porosity is determined by specific gravity measurement. 30% by volume (the same applies hereinafter).

［電池評価］
リチウムイオン二次電池負極活物質としての評価は全ての実施例、比較例ともに同一で、以下の方法・手順にて行った。まず、得られた珪素複合体（又は珪素−炭素複合体）４８部に対して人造黒鉛（平均粒子径Ｄ50＝５μｍ）４２部を加え、混合物を作製した。この混合物にポリフッ化ビニリデンを１０部加え、更にＮ−メチルピロリドンを加え、スラリーとし、このスラリーを厚さ２０μｍの銅箔に塗布し、１２０℃で１時間乾燥後、ローラープレスにより電極を加圧成形し、最終的には２ｃｍ2に打ち抜き、負極とした。
ここで、得られた負極の充放電特性を評価するために、対極にリチウム箔を使用し、非水電解質として六フッ化リンリチウムをエチレンカーボネートと１，２−ジメトキシエタンの１／１（体積比）混合液（ＶＣ：ビニレンカーボネートを２質量％含む）に１モル／Ｌの濃度で溶解した非水電解質溶液を用い、セパレーターに厚さ３０μｍのポリエチレン製微多孔質フィルムを用いた評価用リチウムイオン二次電池を作製した。
作製したリチウムイオン二次電池は、一晩室温で放置した後、二次電池充放電試験装置（（株）ナガノ製）を用いて、テストセルの電圧が０Ｖに達するまで３ｍＡの定電流で充電を行い、０Ｖに達した後は、セル電圧を０Ｖに保つように電流を減少させて充電を行った。そして、電流値が１００μＡを下回った時点で充電を終了した。放電は３ｍＡの定電流で行い、セル電圧が２．０Ｖを上回った時点で放電を終了し、放電容量を求めた。
以上の充放電試験を繰り返し、評価用リチウムイオン二次電池の初期効率測定及び充放電試験５０回を行った。結果を表１に示す。なお、容量は負極膜質量換算である。 [Battery evaluation]
The evaluation as the negative electrode active material of the lithium ion secondary battery was the same in all Examples and Comparative Examples, and was performed by the following methods and procedures. First, 42 parts of artificial graphite (average particle diameter D 50 = 5 μm) was added to 48 parts of the obtained silicon composite (or silicon-carbon composite) to prepare a mixture. 10 parts of polyvinylidene fluoride is added to this mixture, and N-methylpyrrolidone is further added to form a slurry. This slurry is applied to a copper foil having a thickness of 20 μm, dried at 120 ° C. for 1 hour, and then pressed with a roller press. Molded and finally punched out to 2 cm 2 to form a negative electrode.
Here, in order to evaluate the charge / discharge characteristics of the obtained negative electrode, a lithium foil was used as a counter electrode, and lithium hexafluorophosphate was used as a non-aqueous electrolyte with 1/1 (volume) of ethylene carbonate and 1,2-dimethoxyethane. Ratio) A lithium for evaluation using a non-aqueous electrolyte solution dissolved at a concentration of 1 mol / L in a mixed solution (VC: containing 2% by weight of vinylene carbonate), and using a polyethylene microporous film having a thickness of 30 μm as a separator. An ion secondary battery was produced.
The prepared lithium ion secondary battery is left at room temperature overnight and then charged with a constant current of 3 mA until the voltage of the test cell reaches 0 V using a secondary battery charge / discharge test device (manufactured by Nagano Co., Ltd.). After reaching 0V, charging was performed by decreasing the current so as to keep the cell voltage at 0V. Then, the charging was terminated when the current value fell below 100 μA. The discharge was performed at a constant current of 3 mA, and when the cell voltage exceeded 2.0 V, the discharge was terminated and the discharge capacity was determined.
The above charge / discharge test was repeated, and the initial efficiency measurement and the charge / discharge test of the evaluation lithium ion secondary battery were performed 50 times. The results are shown in Table 1. The capacity is in terms of mass of the negative electrode film.

［実施例２］
化学用金属珪素（豪州ＳＩＭＣＯＡ社製低Ａｌ品；Ａｌ：０．０５％，Ｆｅ：０．２１％，Ｃａ：０．００３％）を、ジョークラッシャーで粗砕し、更にヘキサンを分散媒としてボールミル及びビーズミルで平均粒径約１μｍの微粒子にまで粉砕した。得られた懸濁物をろ過し、この状態でヘキサン含有量の測定を行った。この結果を元に、珪素微粉末１００ｇｒに相当するパテ状の珪素−ヘキサン混合物を採取し、ここに、テトラメチルテトラビニルシクロテトラシロキサン〔信越化学工業（株）製ＬＳ−８６７０〕１２ｇｒ、メチル水素シロキサン〔信越化学工業（株）製ＫＦ−９９〕８ｇｒ及び塩化白金酸触媒〔塩化白金酸１％溶液〕０．１ｇｒからなる硬化性シロキサン組成物を添加し、パテ状の状態でよく混合した。その後、６０℃で脱溶剤・プレキュアし、更に２００℃×１時間空気中でキュアした。
こうして得られた塊状のものを、蓋付のアルミナ製容器に入れて、雰囲気コントロール可能な温度プログラム付マッフル炉で窒素雰囲気下にて、１，０００℃×３時間という温度条件で焼成を行った。十分冷却後、クリアランスを２０μｍに設定した粉砕機（マスコロイダー）で粉砕し、平均粒径約１０μｍの珪素複合体（ゼロ価の珪素微粒子含有量は８８質量％であり、空隙率は比重測定より２５容量％であった。）を得た。
こうして得られた珪素複合体の粉末のリチウムイオン二次電池負極活物質としての評価を、実施例１と全く同じ条件で行った。その結果を表１に示す。なお、容量は負極膜質量換算である。 [Example 2]
Metallic silicon for chemical use (low aluminum product manufactured by SIMCOA, Australia; Al: 0.05%, Fe: 0.21%, Ca: 0.003%) is coarsely crushed with a jaw crusher, and then ball mill using hexane as a dispersion medium And it grind | pulverized to the microparticles | fine-particles with an average particle diameter of about 1 micrometer with the bead mill. The obtained suspension was filtered, and the hexane content was measured in this state. Based on this result, a putty-like silicon-hexane mixture corresponding to 100 gr of fine silicon powder was collected, and tetramethyltetravinylcyclotetrasiloxane [LS-8670 manufactured by Shin-Etsu Chemical Co., Ltd.] 12 gr, methyl hydrogen A curable siloxane composition consisting of 8 gr of siloxane [KF-99 manufactured by Shin-Etsu Chemical Co., Ltd.] and 0.1 gr of chloroplatinic acid catalyst [1% solution of chloroplatinic acid] was added and mixed well in a putty state. Thereafter, the solvent was removed and precured at 60 ° C., and further cured in air at 200 ° C. for 1 hour.
The lump obtained in this way was put into an alumina container with a lid and fired under a temperature condition of 1,000 ° C. × 3 hours in a muffle furnace with a temperature program capable of controlling the atmosphere in a nitrogen atmosphere. . After cooling sufficiently, the mixture is pulverized by a pulverizer (mass colloider) with a clearance set to 20 μm, and a silicon composite having an average particle size of about 10 μm (the content of zero-valent silicon fine particles is 88% by mass, and the porosity is determined by measuring the specific gravity. 25% by volume).
Evaluation of the powder of the silicon composite thus obtained as a negative electrode active material for a lithium ion secondary battery was performed under exactly the same conditions as in Example 1. The results are shown in Table 1. The capacity is in terms of mass of the negative electrode film.

［実施例３］
化学用金属珪素（Ｎｏｒｗａｙ ＥＬＫＥＭ製ＨＧグレード品；Ａｌ：０．１０％，Ｆｅ：０．０４％）１００ｇｒにジビニルテトラメチルジシラザン１ｇを密閉容器に採取し、よく混合後１００℃にて１時間加熱し、シリル化を行った。こうして得られた表面処理珪素粉１００ｇｒを採取して、以降、実施例１と全く同様に珪素複合体（ゼロ価の珪素微粒子含有量は８９質量％であり、空隙率は比重測定より３２容量％であった。）を作製し、リチウムイオン二次電池負極活物質としての評価を行った。その結果を表１に示す。なお、容量は負極膜質量換算である。 [Example 3]
1 g of divinyltetramethyldisilazane is collected in 100 g of chemical metallic silicon (HG grade product made by Norway ELKEM; Al: 0.10%, Fe: 0.04%) in a sealed container, and mixed at 100 ° C for 1 hour. Heated to effect silylation. 100 g of the surface-treated silicon powder thus obtained was collected, and thereafter, a silicon composite (the content of zero-valent silicon fine particles was 89% by mass, and the porosity was 32% by volume from the specific gravity measurement) in exactly the same manner as in Example 1. And evaluated as a lithium ion secondary battery negative electrode active material. The results are shown in Table 1. The capacity is in terms of mass of the negative electrode film.

［比較例１］
化学用金属珪素（豪州ＳＩＭＣＯＡ社製低Ａｌ品；Ａｌ：０．０５％，Ｆｅ：０．２１％，Ｃａ：０．００３％）を、ジョークラッシャーで粗砕し、更にヘキサンを分散媒としてボールミル及びビーズミルで平均粒径約１μｍの微粒子にまで粉砕した。得られた懸濁物をろ過し、窒素雰囲気下で脱溶剤後、日清エンジニアリング（株）製空気式精密分級機で粗粒部分をカットし、平均粒径が約０．８μｍの粉末（ゼロ価の珪素微粒子含有量は９８質量％であったが、比重が２．２であることから、ほとんど空隙のないものであった。）を得た。
こうして得られた粗粒部をカットして粒度の揃った珪素微粉末のリチウムイオン二次電池負極活物質としての評価を、実施例１と全く同じ条件で行った。その結果を表１に示す。なお、容量は負極膜質量換算である。 [Comparative Example 1]
Metallic silicon for chemical use (low aluminum product manufactured by SIMCOA, Australia; Al: 0.05%, Fe: 0.21%, Ca: 0.003%) is coarsely crushed with a jaw crusher, and then ball mill using hexane as a dispersion medium And it grind | pulverized to the microparticles | fine-particles with an average particle diameter of about 1 micrometer with the bead mill. The obtained suspension was filtered, and after removing the solvent under a nitrogen atmosphere, the coarse particles were cut with an air precision classifier manufactured by Nissin Engineering Co., Ltd., and a powder having an average particle diameter of about 0.8 μm (zero) The content of the fine silicon fine particles was 98% by mass, but since the specific gravity was 2.2, there was almost no void.
Evaluation of the fine silicon powder having a uniform particle size as a lithium ion secondary battery negative electrode active material was performed under exactly the same conditions as in Example 1 by cutting the coarse portion thus obtained. The results are shown in Table 1. The capacity is in terms of mass of the negative electrode film.

注：一次粒子は、原料微粒子の平均粒径であり、二次粒子は得られた複合体粒子の平均粒径を示す（以下同様）。 Note: The primary particle is the average particle size of the raw material fine particles, and the secondary particle is the average particle size of the obtained composite particles (the same applies hereinafter).

［実施例４］
ブロック状又はフレーク状の酸化珪素（ＳｉＯx：ｘ＝１．０５）を不活性ガス（アルゴン）雰囲気下で１，３００℃、１時間加熱し、珪素と二酸化珪素への不均化を行った。こうして得られたものについてＸ線回折（Ｃｕ−Ｋα）を行い、２θ＝２８．４°のＳｉ（１１１）に帰属される回折線の半価幅からシェーラー法により求めた結晶の大きさは約７５ｎｍであった。このようにして熱処理を行った珪素−二酸化珪素複合物をヘキサンを分散媒としてボールミル及びビーズミルで粉砕し、得られた懸濁物をろ過し、窒素雰囲気下で脱溶剤後、平均粒径が約１μｍの粉末を得た。この珪素−二酸化珪素複合物粉１００ｇｒを、実施例１と同様にテトラメチルテトラビニルシクロテトラシロキサン〔信越化学工業（株）製ＬＳ−８６７０〕１２ｇｒ、メチル水素シロキサン〔信越化学工業（株）製ＫＦ−９９〕８ｇｒ及び塩化白金酸触媒〔塩化白金酸１％溶液〕０．１ｇｒからなる硬化性シロキサン組成物とヘキサン３０ｍｌの混合物に添加し、パテ状の状態でよく混合した。その後、６０℃で脱溶剤・プレキュアした。
塊状のまま、蓋付のアルミナ製容器に入れて、雰囲気コントロール可能な温度プログラム付マッフル炉で窒素雰囲気下にて、３００℃×２時間＋１，０００℃×３時間という温度条件で焼成を行った。十分冷却後、クリアランスを２０μｍに設定した粉砕機（マスコロイダー）で粉砕し、平均粒径約１０μｍの珪素複合体（ゼロ価の珪素微粒子含有量は２８質量％であり、空隙率は比重測定より２８容量％であった。）を得た。
こうして得られた珪素複合体微粉末のリチウムイオン二次電池負極活物質としての評価を、実施例１と全く同じ条件で行った。その結果を表２に示す。なお、容量は負極膜質量換算である。 [Example 4]
Block-like or flaky silicon oxide (SiO x : x = 1.05) was heated at 1,300 ° C. for 1 hour in an inert gas (argon) atmosphere to disproportionate to silicon and silicon dioxide. . The thus obtained product was subjected to X-ray diffraction (Cu-Kα), and the crystal size determined by the Scherrer method from the half-value width of the diffraction line attributed to Si (111) at 2θ = 28.4 ° was about It was 75 nm. The heat-treated silicon-silicon dioxide composite was pulverized with a ball mill and a bead mill using hexane as a dispersion medium, and the resulting suspension was filtered. After removing the solvent under a nitrogen atmosphere, the average particle size was about A 1 μm powder was obtained. In the same manner as in Example 1, 100 gr of this silicon-silicon dioxide composite powder was added to tetramethyltetravinylcyclotetrasiloxane [LS-8670 manufactured by Shin-Etsu Chemical Co., Ltd.] 12 gr, methylhydrogen siloxane [KF manufactured by Shin-Etsu Chemical Co., Ltd.] -99] 8 gr and chloroplatinic acid catalyst [1% solution of chloroplatinic acid] were added to a mixture of curable siloxane composition consisting of 0.1 gr and 30 ml of hexane and mixed well in a putty state. Thereafter, the solvent was removed and precured at 60 ° C.
As a lump, it was placed in an alumina container with a lid and baked under a nitrogen atmosphere in a muffle furnace with a temperature program capable of controlling the atmosphere under a temperature condition of 300 ° C. × 2 hours + 1,000 ° C. × 3 hours. . After cooling sufficiently, it is pulverized with a pulverizer (mass colloider) with a clearance of 20 μm, and a silicon composite having an average particle diameter of about 10 μm (zero-valent silicon fine particle content is 28% by mass, porosity is determined by specific gravity measurement. 28% by volume).
Evaluation of the silicon composite fine powder thus obtained as a lithium ion secondary battery negative electrode active material was performed under exactly the same conditions as in Example 1. The results are shown in Table 2. The capacity is in terms of mass of the negative electrode film.

［実施例５］
ブロック状又はフレーク状の酸化珪素（ＳｉＯx：ｘ＝１．０５）をヘキサンを分散媒としてボールミル及びビーズミルで粉砕し、得られた懸濁物をろ過し、窒素雰囲気下で脱溶剤後、平均粒径が約１μｍの粉末を得た。この酸化珪素粉１００ｇｒを、実施例１と同様にテトラメチルテトラビニルシクロテトラシロキサン〔信越化学工業（株）製ＬＳ−８６７０〕１２ｇｒ、メチル水素シロキサン〔信越化学工業（株）製ＫＦ−９９〕８ｇｒ及び塩化白金酸触媒〔塩化白金酸１％溶液〕０．１ｇｒからなる硬化性シロキサン組成物とヘキサン３０ｍｌの混合物に添加し、パテ状の状態でよく混合した。その後、６０℃で脱溶剤・プレキュアした。
塊状のまま、蓋付のアルミナ製容器に入れて、雰囲気コントロール可能な温度プログラム付マッフル炉で窒素雰囲気下にて、３００℃×２時間＋１，２００℃×３時間という温度条件で加熱し、焼成と酸化珪素組織内の不均化を行った。十分冷却後、クリアランスを２０μｍに設定した粉砕機（マスコロイダー）で粉砕し、平均粒径約１０μｍの珪素複合体（ゼロ価の珪素微粒子含有量は２７質量％であり、空隙率は比重測定より３０容量％であった。）を得た。こうして得られたものについてＸ線回折（Ｃｕ−Ｋα）を行い、２θ＝２８．４°のＳｉ（１１１）に帰属される回折線の半価幅からシェーラー法により求めた結晶の大きさは約６５ｎｍであった。
この珪素複合体微粉末のリチウムイオン二次電池負極活物質としての評価を、実施例１と全く同じ条件で行った。その結果を表２に示す。なお、容量は負極膜質量換算である。 [Example 5]
Block-like or flaky silicon oxide (SiO x : x = 1.05) was pulverized with a ball mill and a bead mill using hexane as a dispersion medium, and the resulting suspension was filtered. After removing the solvent under a nitrogen atmosphere, the average was obtained. A powder having a particle size of about 1 μm was obtained. In the same manner as in Example 1, 100 gr of this silicon oxide powder was added to tetramethyltetravinylcyclotetrasiloxane [LS-8670 manufactured by Shin-Etsu Chemical Co., Ltd.] 12 gr, methylhydrogensiloxane [KF-99 manufactured by Shin-Etsu Chemical Co., Ltd.] 8 gr. And chloroplatinic acid catalyst [1% chloroplatinic acid solution] was added to a mixture of curable siloxane composition consisting of 0.1 gr and 30 ml of hexane and mixed well in a putty state. Thereafter, the solvent was removed and precured at 60 ° C.
It is put in an alumina container with a lid as a lump, heated in a muffle furnace with a temperature program that can control the atmosphere under a nitrogen atmosphere at 300 ° C. × 2 hours + 1,200 ° C. × 3 hours, and fired. And disproportionation in the silicon oxide structure. After cooling sufficiently, the mixture is pulverized by a pulverizer (mass colloider) with a clearance set at 20 μm, and a silicon composite having an average particle size of about 10 μm (the content of zero-valent silicon fine particles is 27% by mass, and the porosity is determined by specific gravity measurement. 30% by volume). The thus obtained product was subjected to X-ray diffraction (Cu-Kα), and the crystal size determined by the Scherrer method from the half-value width of the diffraction line attributed to Si (111) at 2θ = 28.4 ° was about It was 65 nm.
Evaluation of this silicon composite fine powder as a lithium ion secondary battery negative electrode active material was performed under exactly the same conditions as in Example 1. The results are shown in Table 2. The capacity is in terms of mass of the negative electrode film.

［比較例２］
Ｘ線回折的に全く無定形のブロック状又はフレーク状の酸化珪素をヘキサンを分散媒としてボールミル及びビーズミルで粉砕し、得られた懸濁物をろ過し、窒素雰囲気下で脱溶剤後、平均粒径が約１μｍ（ゼロ価の珪素微粒子含有量は３１質量％であるが、空隙を有さないものであった。）の粉末を得た。
この酸化珪素微粉末のリチウムイオン二次電池負極活物質としての評価を、実施例１と全く同じ条件で行った。その結果を表２に示す。なお、容量は負極膜質量換算である。 [Comparative Example 2]
X-ray diffraction completely amorphous block-like or flake-like silicon oxide is pulverized by ball mill and bead mill using hexane as a dispersion medium, the resulting suspension is filtered, and after removing the solvent under nitrogen atmosphere, A powder having a diameter of about 1 μm (the content of zero-valent silicon fine particles was 31% by mass but having no voids) was obtained.
Evaluation of this silicon oxide fine powder as a lithium ion secondary battery negative electrode active material was performed under exactly the same conditions as in Example 1. The results are shown in Table 2. The capacity is in terms of mass of the negative electrode film.

［実施例６］
ブロック状又はフレーク状の酸化珪素をヘキサンを分散媒としてボールミル及びビーズミルで粉砕し、得られた懸濁物をろ過し、窒素雰囲気下で脱溶剤後、平均粒径が約１μｍの粉末を得た。この酸化珪素粉１００ｇｒを、実施例１と同様にテトラメチルテトラビニルシクロテトラシロキサン〔信越化学工業（株）製ＬＳ−８６７０〕１２ｇｒ、メチル水素シロキサン〔信越化学工業（株）製ＫＦ−９９〕８ｇｒ及び塩化白金酸触媒〔塩化白金酸１％溶液〕０．１ｇｒからなる硬化性シロキサン組成物とヘキサン３０ｍｌの混合物に添加し、パテ状の状態でよく混合した。６０℃で脱溶剤及び２００℃×１時間熱硬化した。その後、クリアランスを２０μｍに設定した粉砕機（マスコロイダー）で粉砕し、平均粒径約１０μｍの含珪素造粒粒子（ゼロ価の珪素微粒子含有量は２８質量％であり、空隙率は比重測定より２５容量％であった。）を得た。
この含珪素造粒粒子を縦型管状炉（内径約５０ｍｍφ）を用いて、メタン−アルゴン混合ガス通気下で１，２００℃、３時間の熱ＣＶＤを行った。こうして、得られた導電性珪素複合体をらいかい器で解砕した。得られた導電性珪素複合体粒子の炭素量は１５％、活性珪素量は２８．１％、平均粒径は１３μｍであり、シェーラー法により求めた二酸化珪素中に分散した珪素の結晶の大きさは約６０ｎｍであった。 [Example 6]
Block or flaky silicon oxide was pulverized with a ball mill and bead mill using hexane as a dispersion medium, the resulting suspension was filtered, and after removing the solvent in a nitrogen atmosphere, a powder having an average particle size of about 1 μm was obtained. . In the same manner as in Example 1, 100 gr of this silicon oxide powder was added to tetramethyltetravinylcyclotetrasiloxane [LS-8670 manufactured by Shin-Etsu Chemical Co., Ltd.] 12 gr, methylhydrogensiloxane [KF-99 manufactured by Shin-Etsu Chemical Co., Ltd.] 8 gr. And chloroplatinic acid catalyst [1% chloroplatinic acid solution] was added to a mixture of curable siloxane composition consisting of 0.1 gr and 30 ml of hexane and mixed well in a putty state. Solvent removal at 60 ° C. and heat curing at 200 ° C. for 1 hour. After that, it was pulverized by a pulverizer (mass colloider) with a clearance set at 20 μm, and silicon-containing granulated particles having an average particle diameter of about 10 μm (the content of zero-valent silicon fine particles was 28% by mass, and the porosity was determined from specific gravity measurement. 25% by volume).
The silicon-containing granulated particles were subjected to thermal CVD at 1,200 ° C. for 3 hours under a methane-argon mixed gas flow using a vertical tubular furnace (inner diameter: about 50 mmφ). Thus, the obtained conductive silicon composite was crushed with a sieve. The obtained conductive silicon composite particles had a carbon content of 15%, an active silicon content of 28.1% and an average particle size of 13 μm. The size of silicon crystals dispersed in silicon dioxide determined by the Scherrer method Was about 60 nm.

［電池評価］
リチウムイオン二次電池負極活物質としての評価は実施例６、比較例３ともに同一で、以下の方法・手順にて行った。まず、得られた炭素コート珪素複合体に人造黒鉛（平均粒子径Ｄ50＝５μｍ）を加え、人造黒鉛の炭素と蒸着した珪素複合体中のフリー炭素が合計４０％となるように加え、混合物を作製した。この混合物にポリフッ化ビニリデンを１０％加え、更にＮ−メチルピロリドンを加え、スラリーとし、このスラリーを厚さ２０μｍの銅箔に塗布し、１２０℃で１時間乾燥後、ローラープレスにより電極を加圧成形し、最終的には２ｃｍ2に打ち抜き、負極とした。以下、実施例１に記載の方法と全く同一の手順で行った。
こうして得られた珪素複合体微粉末のリチウムイオン二次電池負極活物質としての評価結果を表３に示す。なお、容量は負極膜質量換算である。 [Battery evaluation]
Evaluation as a lithium ion secondary battery negative electrode active material was the same in Example 6 and Comparative Example 3, and was performed by the following method and procedure. First, artificial graphite (average particle diameter D 50 = 5 μm) was added to the obtained carbon-coated silicon composite, and the carbon of the artificial graphite and the free carbon in the deposited silicon composite were added to a total of 40%, and the mixture Was made. 10% polyvinylidene fluoride is added to this mixture, and N-methylpyrrolidone is further added to form a slurry. This slurry is applied to a copper foil having a thickness of 20 μm, dried at 120 ° C. for 1 hour, and then pressed with a roller press. Molded and finally punched out to 2 cm 2 to form a negative electrode. Thereafter, the same procedure as described in Example 1 was performed.
Table 3 shows the evaluation results of the silicon composite fine powder thus obtained as a negative electrode active material for a lithium ion secondary battery. The capacity is in terms of mass of the negative electrode film.

［比較例３］
実施例６と同様に、ブロック状又はフレーク状の酸化珪素をヘキサンを分散媒としてボールミル及びビーズミルで粉砕し、得られた懸濁物をろ過し、窒素雰囲気下で脱溶剤後、平均粒径が約１μｍの粉末（空隙率は０容量％）を得た。この酸化珪素粉１００ｇｒを、縦型管状炉（内径約５０ｍｍφ）を用いて、メタン−アルゴン混合ガス通気下で１，２００℃、５時間の熱ＣＶＤを行った。こうして、得られた導電性珪素複合体をらいかい器で解砕した。得られた導電性珪素複合体粒子の炭素量は１７％、ゼロ価の活性珪素量は２５％、平均粒径は１３μｍであり、シェーラー法により求めた二酸化珪素中に分散した珪素の結晶の大きさは約６５ｎｍであった。
この珪素複合体微粒子のリチウムイオン二次電池負極活物質としての評価を、実施例６と全く同じ条件で行った。その結果を表３に示す。なお、容量は負極膜質量換算である。 [Comparative Example 3]
In the same manner as in Example 6, block or flake silicon oxide was pulverized with a ball mill and a bead mill using hexane as a dispersion medium, the obtained suspension was filtered, and after removing the solvent under a nitrogen atmosphere, the average particle size was reduced. About 1 μm powder (porosity of 0% by volume) was obtained. 100 gr of this silicon oxide powder was subjected to thermal CVD at 1,200 ° C. for 5 hours under a methane-argon mixed gas flow using a vertical tubular furnace (inner diameter: about 50 mmφ). Thus, the obtained conductive silicon composite was crushed with a sieve. The obtained conductive silicon composite particles had a carbon content of 17%, a zero-valent active silicon content of 25%, an average particle size of 13 μm, and the size of silicon crystals dispersed in silicon dioxide determined by the Scherrer method. The thickness was about 65 nm.
Evaluation of the silicon composite fine particles as a lithium ion secondary battery negative electrode active material was performed under exactly the same conditions as in Example 6. The results are shown in Table 3. The capacity is in terms of mass of the negative electrode film.

［実施例７］
化学用金属珪素（豪州ＳＩＭＣＯＡ社製低Ａｌ品；Ａｌ：０．０５％，Ｆｅ：０．２１％，Ｃａ：０．００３％）を、ジョークラッシャーで粗砕し、更にヘキサンを分散媒としてボールミル及びビーズミルで平均粒径約１μｍの微粒子にまで粉砕した。得られた懸濁物をろ過し、窒素雰囲気下で脱溶剤後、日清エンジニアリング（株）製空気式精密分級機で粗粒部分をカットし、平均粒径が約０．８μｍの粉末を得た。この珪素微粉末１００ｇｒと大阪ガスケミカル株式会社製球状グラファイト粉ＭＣＭＢ０６−２８（平均粒子径：６μｍ）８０ｇｒを混合し、ここに予め調製した、テトラメチルテトラビニルシクロテトラシロキサン〔信越化学工業（株）製ＬＳ−８６７０〕１２ｇｒ、メチル水素シロキサン〔信越化学工業（株）製ＫＦ−９９〕８ｇｒ及び塩化白金酸触媒〔塩化白金酸１％溶液〕０．１ｇｒからなる硬化性シロキサン組成物とヘキサン３０ｍｌの混合物を添加し、パテ状の状態でよく混合した。その後、６０℃で脱溶剤・プレキュアした。
塊状のまま、蓋付のアルミナ製容器に入れて、雰囲気コントロール可能な温度プログラム付マッフル炉で窒素雰囲気下にて、３００℃×２時間＋１，０００℃×３時間という温度条件で焼成を行った。十分冷却後、クリアランスを２０μｍに設定した粉砕機（マスコロイダー）で粉砕し、平均粒径約１５μｍの珪素複合体（ゼロ価の珪素微粒子含有量が５５質量％、空隙率が比重測定より２８容量％、カーボン含有量が４０質量％）を得た。
上記充放電試験を繰り返し、評価用リチウムイオン二次電池の初期効率測定及び充放電試験５０回を行った。結果を表４に示す。なお、容量は負極膜重量換算である。 [Example 7]
Metallic silicon for chemical use (low aluminum product manufactured by SIMCOA, Australia; Al: 0.05%, Fe: 0.21%, Ca: 0.003%) is coarsely crushed with a jaw crusher, and then ball mill using hexane as a dispersion medium And it grind | pulverized to the microparticles | fine-particles with an average particle diameter of about 1 micrometer with the bead mill. The obtained suspension was filtered, and after removing the solvent under a nitrogen atmosphere, the coarse particles were cut with an air precision classifier manufactured by Nissin Engineering Co., Ltd. to obtain a powder having an average particle size of about 0.8 μm. It was. 100 gr of this silicon fine powder and 80 gr of spherical graphite powder MCMB06-28 (average particle size: 6 μm) manufactured by Osaka Gas Chemical Co., Ltd. were mixed, and tetramethyltetravinylcyclotetrasiloxane [Shin-Etsu Chemical Co., Ltd.] LS-8670 manufactured by LS-8670], 12 grams of methyl hydrogen siloxane [KF-99 manufactured by Shin-Etsu Chemical Co., Ltd.] 8 grams and chloroplatinic acid catalyst [1% solution of chloroplatinic acid] 0.1 gr and 30 ml of hexane. The mixture was added and mixed well in a putty state. Thereafter, the solvent was removed and precured at 60 ° C.
As a lump, it was placed in an alumina container with a lid and baked under a nitrogen atmosphere in a muffle furnace with a temperature program capable of controlling the atmosphere under a temperature condition of 300 ° C. × 2 hours + 1,000 ° C. × 3 hours. . After cooling sufficiently, the mixture was pulverized with a pulverizer (mass colloider) with a clearance of 20 μm, and a silicon composite having an average particle size of about 15 μm (zero-valent silicon fine particle content was 55% by mass, porosity was 28 volumes from specific gravity measurement) %, And the carbon content was 40% by mass).
The charge / discharge test was repeated, and the initial efficiency measurement and charge / discharge test of the evaluation lithium ion secondary battery were performed 50 times. The results are shown in Table 4. The capacity is in terms of the weight of the negative electrode film.

［実施例８］
実施例７で記載した方法で、平均粒径が約０．８μｍの珪素粉末を得、この珪素微粉末１００ｇｒとＳＣＥ社製鱗片状合成グラファイト粉ＳＧＰ１０（平均粒子径：１０μｍ）８０ｇｒを混合し、ここに予め調製した、テトラメチルテトラビニルシクロテトラシロキサン〔信越化学工業（株）製ＬＳ−８６７０〕１２ｇｒ、メチル水素シロキサン〔信越化学工業（株）製ＫＦ−９９〕８ｇｒ及び塩化白金酸触媒〔塩化白金酸１％溶液〕０．１ｇｒからなる硬化性シロキサン組成物とヘキサン３０ｍｌの混合物を添加し、パテ状の状態でよく混合した。その後、６０℃で脱溶剤・プレキュアした。塊状のまま、蓋付のアルミナ製容器に入れて、雰囲気コントロール可能な温度プログラム付マッフル炉で窒素雰囲気下にて、３００℃×２時間＋１，０００℃×３時間という温度条件で焼成を行った。十分冷却後、クリアランスを２０μｍに設定した粉砕機（マスコロイダー）で粉砕し、平均粒径約１５μｍの珪素−炭素複合体（ゼロ価の珪素微粒子含有量が５３質量％、空隙率が比重測定より２５容量％、カーボン含有量が４２質量％）を得た。
このリチウムイオン二次電池負極活物質としての評価を、実施例７と全く同じ条件で行った。その結果を表４に示す。なお、容量は負極膜重量換算である。 [Example 8]
By the method described in Example 7, a silicon powder having an average particle diameter of about 0.8 μm was obtained, and 100 gr of this silicon fine powder was mixed with Scr scale synthetic graphite powder SGP10 (average particle diameter: 10 μm) 80 gr. Tetramethyltetravinylcyclotetrasiloxane [LS-8670 manufactured by Shin-Etsu Chemical Co., Ltd.] 12 gr, methylhydrogen siloxane [KF-99 manufactured by Shin-Etsu Chemical Co., Ltd.] 8 gr and chloroplatinic acid catalyst [salt] Platinum acid 1% solution] A mixture of a curable siloxane composition consisting of 0.1 gr and 30 ml of hexane was added and mixed well in a putty state. Thereafter, the solvent was removed and precured at 60 ° C. As a lump, it was placed in an alumina container with a lid and baked under a nitrogen atmosphere in a muffle furnace with a temperature program capable of controlling the atmosphere under a temperature condition of 300 ° C. × 2 hours + 1,000 ° C. × 3 hours. . After sufficiently cooling, the mixture is pulverized with a pulverizer (mass colloider) with a clearance set at 20 μm, and a silicon-carbon composite having an average particle size of about 15 μm (zero-valent silicon fine particle content is 53 mass%, porosity is measured by specific gravity) 25% by volume and a carbon content of 42% by mass).
Evaluation as this lithium ion secondary battery negative electrode active material was performed under exactly the same conditions as in Example 7. The results are shown in Table 4. The capacity is in terms of the weight of the negative electrode film.

［実施例９］
実施例７で作製した平均粒子径約１５μｍの珪素−炭素複合体約１００ｇｒを内径約３０ｍｍのアルミナ製縦型反応機に入れ、アルゴン気流下で予め１，１５０℃に昇温したのち、メタン−アルゴン（メタン３０％）に切り替え、３時間熱ＣＶＤを行った。冷却後、らいかい機で解砕し、平均粒子径約１５μｍの導電性珪素−炭素系複合体（ゼロ価の珪素量：４９質量％，グラファイト：３６質量％，ＣＶＤ炭素：１４質量％（ＣＶＤ後の空隙率は測定困難））を得た。
このリチウムイオン二次電池負極活物質としての評価を、実施例７と全く同じ条件で行った。その結果を表４に示す。なお、容量は負極膜重量換算である。 [Example 9]
About 100 gr of the silicon-carbon composite having an average particle diameter of about 15 μm prepared in Example 7 was placed in an alumina vertical reactor having an inner diameter of about 30 mm, and the temperature was raised to 1,150 ° C. in advance under an argon stream. Switching to argon (methane 30%), thermal CVD was performed for 3 hours. After cooling, the mixture was crushed with a cracking machine, and a conductive silicon-carbon composite having an average particle diameter of about 15 μm (zero-valent silicon content: 49 mass%, graphite: 36 mass%, CVD carbon: 14 mass% (CVD The later porosity was difficult to measure)).
Evaluation as this lithium ion secondary battery negative electrode active material was performed under exactly the same conditions as in Example 7. The results are shown in Table 4. The capacity is in terms of the weight of the negative electrode film.

［比較例４］
化学用金属珪素（豪州ＳＩＭＣＯＡ社製低Ａｌ品；Ａｌ：０．０５％，Ｆｅ：０．２１％，Ｃａ：０．００３％）を、ジョークラッシャーで粗砕し、更にヘキサンを分散媒としてボールミル及びビーズミルで平均粒径約１μｍの微粒子にまで粉砕した。得られた懸濁物をろ過し、窒素雰囲気下で脱溶剤後、日清エンジニアリング（株）製空気式精密分級機で粗粒部分をカットし、平均粒径が約０．８μｍの粉末（この粉末は造粒していないため、空隙を有さないものである）を得た。
こうして得られた粗粒部をカットして粒度の揃った珪素微粉末を実施例に従って、メタンによって熱ＣＶＤを行い、炭素量約１５％の炭素被覆珪素粉を得た。このリチウムイオン二次電池負極活物質としての評価を、実施例７と全く同じ条件で行った。その結果を表４に示す。なお、容量は負極膜重量換算である。 [Comparative Example 4]
Metallic silicon for chemical use (low aluminum product manufactured by SIMCOA, Australia; Al: 0.05%, Fe: 0.21%, Ca: 0.003%) is coarsely crushed with a jaw crusher, and then ball mill using hexane as a dispersion medium And it grind | pulverized to the microparticles | fine-particles with an average particle diameter of about 1 micrometer with the bead mill. The obtained suspension was filtered, and after removing the solvent under a nitrogen atmosphere, the coarse particles were cut with an air precision classifier manufactured by Nissin Engineering Co., Ltd. Since the powder is not granulated, it has no voids).
The coarse particles thus obtained were cut, and the silicon fine powder having a uniform particle size was subjected to thermal CVD with methane according to the example to obtain a carbon-coated silicon powder having a carbon content of about 15%. Evaluation as this lithium ion secondary battery negative electrode active material was performed under exactly the same conditions as in Example 7. The results are shown in Table 4. The capacity is in terms of the weight of the negative electrode film.

本発明の珪素複合体のイメージ図である。It is an image figure of the silicon composite of this invention. 珪素−炭素複合体のイメージ図である。It is an image figure of a silicon-carbon composite. 透過電子顕微鏡による珪素系複合体と炭素層界面の融合状態観察例を示した図である。It is the figure which showed the example of a fusion state observation of the silicon system composite_body | complex and carbon layer interface by a transmission electron microscope. （Ａ）、（Ｂ）はそれぞれ珪素複合体の焼結状態での断面ＳＥＭ写真である。(A) and (B) are cross-sectional SEM photographs in the sintered state of the silicon composite, respectively. （Ａ）、（Ｂ）はそれぞれ球状グラファイト（１０μｍ）を配合した場合における珪素−炭素複合体断面のＳＥＭ写真である。(A) and (B) are SEM photographs of the cross section of the silicon-carbon composite when spherical graphite (10 μm) is blended. （Ａ）、（Ｂ）はそれぞれ鱗片状グラファイト（６μｍ）を配合した場合における珪素−炭素複合体断面のＳＥＭ写真である。(A) and (B) are SEM photographs of the cross section of the silicon-carbon composite when scaly graphite (6 μm) is blended. 珪素−炭素複合体断面の反射電子像（組成像）であり、（Ａ）は球状グラファイトを配合した場合、（Ｂ）は鱗片状グラファイトを配合した場合である。It is the reflected electron image (composition image) of a silicon-carbon composite cross section, (A) is a case where spherical graphite is mix | blended, (B) is a case where scaly graphite is mix | blended.

符号の説明Explanation of symbols

１ 珪素複合体粒子
２ 珪素−炭素複合体粒子
１１ 珪素又は珪素合金
１２ 珪素系無機化合物のバインダー
１３ 空隙
１４ 炭素微粒子
DESCRIPTION OF SYMBOLS 1 Silicon composite particle 2 Silicon-carbon composite particle 11 Silicon or silicon alloy 12 Binder of silicon-based inorganic compound 13 Void 14 Carbon fine particle

Claims (21)

珪素と、珪素合金又は酸化珪素の微粒子と、球形又は鱗片状の天然又は合成グラファイトである炭素微粒子とを、有機珪素化合物又はその混合物と共に焼結することによって得られる粒子であって、上記有機珪素化合物又はその混合物が焼結されることによって形成される珪素系無機化合物をバインダーとしてこの中に珪素又は珪素合金微粒子及び炭素微粒子が分散されていると共に、該粒子内に空隙が存在する構造を有することを特徴とする、リチウムイオン二次電池用珪素複合体粒子。 Particles obtained by sintering silicon , silicon alloy or silicon oxide fine particles, and carbon fine particles that are spherical or scale-like natural or synthetic graphite, together with an organic silicon compound or a mixture thereof, Silicon or silicon alloy fine particles and carbon fine particles are dispersed in a silicon-based inorganic compound formed by sintering a compound or a mixture thereof as a binder, and voids exist in the particles. A silicon composite particle for a lithium ion secondary battery . 珪素、珪素合金又は酸化珪素の一次粒子の大きさが１００ｎｍ〜１０μｍであり、炭素の一次粒子の大きさが１００ｎｍ〜２０μｍであり、珪素系無機化合物がＳｉ−Ｃ−ＯもしくはＳｉ−Ｃ−Ｎ系コンポジット、ＳｉＮx、ＳｉＯy、ＳｉＣz（但し、ｘは０＜ｘ≦４／３、ｙは０＜ｙ≦２、ｚは０＜ｚ≦１の正数である）又はこれらの混合物であることを特徴とする請求項１記載のリチウムイオン二次電池用珪素複合体粒子。 The primary particle size of silicon, silicon alloy or silicon oxide is 100 nm to 10 μm, the primary particle size of carbon is 100 nm to 20 μm, and the silicon-based inorganic compound is Si—C—O or Si—C—N. Composite, SiN x , SiO y , SiC z (where x is 0 <x ≦ 4/3, y is 0 <y ≦ 2, z is a positive number of 0 <z ≦ 1) or a mixture thereof The silicon composite particle for a lithium ion secondary battery according to claim 1, wherein 有機珪素化合物又はその混合物が、架橋基を有する反応性有機珪素化合物又は硬化性ポリシロキサン組成物であることを特徴とする請求項１又は２記載のリチウムイオン二次電池用珪素複合体粒子。 Organosilicon compounds or mixtures thereof, the reactive organic silicon compound or a curable polysiloxane composition according to claim 1 or 2 for a lithium ion secondary battery silicon composite particles wherein that having a crosslinkable group. 架橋基を有する反応性有機珪素化合物が、下記一般式（１）〜（５）で示されるシラン又はシロキサンの１種又は２種以上である請求項３記載のリチウムイオン二次電池用珪素複合体粒子。
（式中、Ｒ1〜Ｒ7は、独立して水素原子、水酸基、加水分解性基、又は１価炭化水素基を示すが、上記式（１）〜（５）の各化合物において、珪素原子に結合する置換基の少なくとも２個は水素原子、水酸基、加水分解性基又は脂肪族不飽和炭化水素基である。ｍ、ｎ、ｋは０〜２，０００、ｐ、ｑは０〜１０であるが、ｐ、ｑは同時に０になることはない。） 4. The silicon composite for lithium ion secondary battery according to claim 3, wherein the reactive organosilicon compound having a crosslinking group is one or more of silanes or siloxanes represented by the following general formulas (1) to (5). particle.
(Wherein R 1 to R 7 independently represent a hydrogen atom, a hydroxyl group, a hydrolyzable group, or a monovalent hydrocarbon group, but in each compound of the above formulas (1) to (5), a silicon atom At least two of the substituents bonded to are hydrogen atom, hydroxyl group, hydrolyzable group or aliphatic unsaturated hydrocarbon group, m, n and k are 0 to 2,000, p and q are 0 to 10. (However, p and q are not 0 at the same time.) 架橋基を有する反応性有機珪素化合物又はその混合物が、平均式ＣhＨiＳｉＯjＮk（ｈ、ｉ、ｊは正数、ｋは０又は正数）で表され、架橋点が珪素原子４個に対して少なくとも１個有し、かつ（ｈ−ｊ）が０より大きなシラン又はシロキサンであることを特徴とする請求項３記載のリチウムイオン二次電池用珪素複合体粒子。 A reactive organosilicon compound having a crosslinkable group or a mixture thereof is represented by the average formula C h H i SiO j N k (h, i, j are positive numbers, k is 0 or a positive number), and the crosslink point is a silicon atom. The silicon composite particle for a lithium ion secondary battery according to claim 3 , wherein the silane or siloxane has at least one for four and (hj) is greater than zero. 硬化性ポリシロキサン組成物が、付加反応硬化型オルガノポリシロキサン組成物であることを特徴とする請求項３記載のリチウムイオン二次電池用珪素複合体粒子。 4. The silicon composite particle for a lithium ion secondary battery according to claim 3, wherein the curable polysiloxane composition is an addition reaction curable organopolysiloxane composition. 粒子内の空隙率が１〜７０体積％である請求項１〜６のいずれか１項記載のリチウムイオン二次電池用珪素複合体粒子。 Any one lithium ion secondary battery silicon composite particles according to claim 1-6 porosity in the particles is 1 to 70% by volume. 請求項１〜７のいずれか１項記載の珪素複合体粒子の表面を炭素でコーティングしてなることを特徴とするリチウムイオン二次電池用導電性珪素複合体粒子。 Claim 1-7 any one lithium ion secondary battery conductive silicon composite particles the surface of the silicon composite particles characterized by being coated with carbon according to. 珪素、珪素合金又は酸化珪素の微粒子を有機珪素化合物又はその混合物と共に焼結し、造粒して、上記有機珪素化合物又はその混合物が焼結されることによって形成される珪素系無機化合物をバインダーとしてこの中に珪素又は珪素合金微粒子が分散されていると共に、内部に空隙が存在する構造を有する珪素複合体粒子を得ることを特徴とする、リチウムイオン二次電池用珪素複合体粒子の製造方法。 Silicon, silicon alloy or silicon oxide fine particles are sintered together with an organic silicon compound or a mixture thereof, granulated, and a silicon-based inorganic compound formed by sintering the organic silicon compound or the mixture thereof as a binder. A method for producing silicon composite particles for a lithium ion secondary battery, wherein silicon composite particles having a structure in which silicon or silicon alloy fine particles are dispersed therein and voids are present therein are obtained. 珪素、珪素合金又は酸化珪素の一次粒子の大きさが１００ｎｍ〜１０μｍであり、珪素系無機化合物がＳｉ−Ｃ−ＯもしくはＳｉ−Ｃ−Ｎ系コンポジット、ＳｉＮx、ＳｉＯy、ＳｉＣz（但し、ｘは０＜ｘ≦４／３、ｙは０＜ｙ≦２、ｚは０＜ｚ≦１の正数である）又はこれらの混合物であることを特徴とする請求項９記載のリチウムイオン二次電池用珪素複合体粒子の製造方法。 The primary particle size of silicon, silicon alloy or silicon oxide is 100 nm to 10 μm, and the silicon-based inorganic compound is Si—C—O or Si—C—N based composite, SiN x , SiO y , SiC z (provided that x is 0 <x ≦ 4/3, y is 0 <y ≦ 2, z is 0 <z ≦ 1 for a positive number) or lithium-ion secondary of claim 9, wherein the mixtures thereof A method for producing silicon composite particles for a secondary battery . 珪素、珪素合金又は酸化珪素の微粒子及び炭素微粒子を有機珪素化合物又はその混合物と共に焼結し、造粒して、上記有機珪素化合物又はその混合物が焼結されることによって形成される珪素系無機化合物をバインダーとしてこの中に珪素又は珪素合金微粒子及び炭素微粒子が分散されていると共に、内部に空隙が存在する構造を有する珪素−炭素複合体粒子を得ることを特徴とするリチウムイオン二次電池用珪素複合体粒子の製造方法。 Silicon inorganic compound formed by sintering and granulating silicon, silicon alloy or silicon oxide fine particles and carbon fine particles together with an organic silicon compound or a mixture thereof, and sintering the organic silicon compound or the mixture thereof. Silicon for lithium ion secondary battery , characterized in that silicon or silicon alloy fine particles and carbon fine particles are dispersed therein and silicon-carbon composite particles having a structure in which voids exist are obtained. A method for producing composite particles. 珪素、珪素合金又は酸化珪素の一次粒子の大きさが１００ｎｍ〜１０μｍであり、炭素の一次粒子の大きさが１００ｎｍ〜２０μｍであり、珪素系無機化合物がＳｉ−Ｃ−ＯもしくはＳｉ−Ｃ−Ｎ系コンポジット、ＳｉＮx、ＳｉＯy、ＳｉＣz（但し、ｘは０＜ｘ≦４／３、ｙは０＜ｙ≦２、ｚは０＜ｚ≦１の正数である）又はこれらの混合物であることを特徴とする請求項１１記載のリチウムイオン二次電池用珪素複合体粒子の製造方法。 The primary particle size of silicon, silicon alloy or silicon oxide is 100 nm to 10 μm, the primary particle size of carbon is 100 nm to 20 μm, and the silicon-based inorganic compound is Si—C—O or Si—C—N. Composite, SiN x , SiO y , SiC z (where x is 0 <x ≦ 4/3, y is 0 <y ≦ 2, z is a positive number of 0 <z ≦ 1) or a mixture thereof the process according to claim 1 1 for a lithium ion secondary battery silicon composite particles, wherein the certain. 炭素粒子が球形又は鱗片状の天然又は合成グラファイトである請求項１１又は１２記載のリチウムイオン二次電池用珪素複合体粒子の製造方法。 The method according to claim 1 1 or 1 2 for a lithium ion secondary battery silicon composite particles according carbon particles are spherical or scale-like natural or synthetic graphite. 有機珪素化合物又はその混合物が、架橋基を有する反応性有機珪素化合物又は硬化性ポリシロキサン組成物であり、これを珪素又は珪素合金微粒子と混合した後、熱硬化又は触媒反応により硬化させて架橋物とし、更に不活性気流中５００〜１，４００℃の温度範囲で加熱、焼結させて無機化し、これを０．５〜３０μｍに再粉砕することを特徴とする請求項９〜１３のいずれか１項記載のリチウムイオン二次電池用珪素複合体の製造方法。 The organosilicon compound or a mixture thereof is a reactive organosilicon compound or a curable polysiloxane composition having a crosslinkable group, and after this is mixed with silicon or silicon alloy fine particles, it is cured by thermal curing or catalytic reaction to be crosslinked. and then, further heated at a temperature in the range of 500～1,400 ° C. in an inert gas stream, and mineralized by sintering, claim 9 to 13, characterized in that the reground this 0.5~30μm A method for producing a silicon composite for a lithium ion secondary battery according to claim 1. 架橋基を有する反応性有機珪素化合物が、下記一般式（１）〜（５）で示されるシラン又はシロキサンの１種又は２種以上である請求項１４記載のリチウムイオン二次電池用珪素複合体粒子の製造方法。
（式中、Ｒ1〜Ｒ7は、独立して水素原子、水酸基、加水分解性基、又は１価炭化水素基を示すが、上記式（１）〜（５）の各化合物において、珪素原子に結合する置換基の少なくとも２個は水素原子、水酸基、加水分解性基又は脂肪族不飽和炭化水素基である。ｍ、ｎ、ｋは０〜２，０００、ｐ、ｑは０〜１０であるが、ｐ、ｑは同時に０になることはない。） Reactive organic silicon compound having a crosslinking group is represented by the following general formula (1) to (5) is a silane or siloxane one or more of claims 1 to 4 silicon for lithium ion secondary battery composite according represented by A method for producing body particles.
(Wherein R 1 to R 7 independently represent a hydrogen atom, a hydroxyl group, a hydrolyzable group, or a monovalent hydrocarbon group, but in each compound of the above formulas (1) to (5), a silicon atom At least two of the substituents bonded to are hydrogen atom, hydroxyl group, hydrolyzable group or aliphatic unsaturated hydrocarbon group, m, n and k are 0 to 2,000, p and q are 0 to 10. (However, p and q are not 0 at the same time.) 架橋基を有する反応性有機珪素化合物又はその混合物が、平均式ＣhＨiＳｉＯjＮk（ｈ、ｉ、ｊは正数、ｋは０又は正数）で表され、架橋点が珪素原子４個に対して少なくとも１個有し、かつ（ｈ−ｊ）が０より大きなシラン又はシロキサンであることを特徴とする請求項１４記載のリチウムイオン二次電池用珪素複合体粒子の製造方法。 A reactive organosilicon compound having a crosslinkable group or a mixture thereof is represented by the average formula C h H i SiO j N k (h, i, j are positive numbers, k is 0 or a positive number), and the crosslink point is a silicon atom. having at least one for four, and a manufacturing method of (h-j) is according to claim 1 4 for a lithium ion secondary battery silicon composite particles wherein the a major silanes or siloxanes from 0 . 硬化性ポリシロキサン組成物が、付加反応硬化型オルガノポリシロキサン組成物であることを特徴とする請求項１４記載のリチウムイオン二次電池用珪素複合体粒子の製造方法。 Method for producing a curable polysiloxane composition, addition-curable organopolysiloxane characterized in that it is a composition according to claim 1 4 for a lithium ion secondary battery silicon composite particles according. 珪素又は珪素合金微粒子の表面を予めシランカップリング剤、その（部分）加水分解縮合物、シリル化剤、シリコーンレジンから選ばれる１種又は２種以上の表面処理剤で処理することを特徴とする請求項９〜１７のいずれか１項記載のリチウムイオン二次電池用珪素複合体粒子の製造方法。 The surface of silicon or silicon alloy fine particles is treated in advance with one or more surface treatment agents selected from silane coupling agents, (partial) hydrolysis condensates, silylating agents, and silicone resins. The manufacturing method of the silicon composite particle for lithium ion secondary batteries of any one of Claims 9-17 . 請求項９〜１８のいずれか１項記載の製造方法によって得られた珪素複合体粒子を有機物ガス及び／又は蒸気を含む雰囲気下、８００〜１，４００℃の温度域で熱処理して、上記珪素複合体粒子の表面をコーティングすることを特徴とする、リチウムイオン二次電池用導電性珪素複合体粒子の製造方法。 The silicon composite particles obtained by the production method according to any one of claims 9 to 18 are heat-treated in a temperature range of 800 to 1,400 ° C in an atmosphere containing an organic gas and / or vapor, and the silicon A method for producing conductive silicon composite particles for a lithium ion secondary battery , wherein the surface of the composite particles is coated. 請求項１〜８のいずれか１項記載の珪素複合体粒子を用いた非水電解質二次電池用負極材。 The negative electrode material for nonaqueous electrolyte secondary batteries using the silicon composite particle of any one of Claims 1-8 . 請求項１〜８のいずれか１項記載の珪素複合体粒子と導電剤の混合物であって、混合物中の導電剤が１〜６０質量％であり、かつ混合物中の全炭素量が２５〜９０質量％である混合物を用いた非水電解質二次電池用負極材。 A mixture of silicon composite particles and a conductive agent according to any one of claims 1 to 8, wherein the conductive agent in the mixture is 1 to 60% by mass and the total carbon content in the mixture is 25 to 90. A negative electrode material for a non-aqueous electrolyte secondary battery using a mixture having a mass%.
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